KR20190113612A - Hydrogen barrier agent, hydrogen barrier film forming composition, hydrogen barrier film, method for producing hydrogen barrier film, and electronic element - Google Patents

Abstract

The present invention provides: a hydrogen barrier agent capable of imparting hydrogen barrier performance to various materials; a hydrogen barrier film forming composition including the hydrogen barrier agent; a hydrogen barrier film including the hydrogen barrier agent; a method for manufacturing the hydrogen barrier film, which uses the hydrogen barrier film forming composition; and an electronic element provided with the hydrogen barrier film. A compound having a specific structure including an imidazolyl group is used as the hydrogen barrier agent. Furthermore, the hydrogen barrier film forming composition is prepared by blending the hydrogen barrier agent into the base material component. In addition, the hydrogen barrier film is formed using the hydrogen barrier film forming composition.

Description

HYDROGEN BARRIER AGENT, HYDROGEN BARRIER FILM FORMING COMPOSITION, HYDROGEN BARRIER FILM, METHOD FOR PRODUCING HYDROGEN BARRIER FILM, AND ELECTRONIC ELEMENT}

The present invention relates to a hydrogen barrier agent, a composition for forming a hydrogen barrier film, a hydrogen barrier film, a method for producing a hydrogen barrier film, and an electronic device.

Conventionally, various functional films have been formed in various electronic devices. Among electronic devices, development of organic electronic devices is progressing along with progress of the development of a conductive organic material and an organic semiconductor. Representative examples of such organic electronic devices include organic EL devices.

When an electronic element is an organic electroluminescent element, as a functional film, a passivation film, a transparent electrode film, a transparent insulating layer, a planarization film, an organic light emitting film, a protective film, etc. are mentioned, for example.

Electronic devices often include a TFT to drive the device like an organic EL device. In addition, the electronic device is often provided with wiring made of metal such as copper. Here, the TFT may be impaired in function due to a reduction reaction by contact with hydrogen gas, and the electrical characteristics may change due to reduction by hydrogen gas in the metal wiring.

On the other hand, among the materials of the functional film in an electronic element, there exists a material which discharge | releases hydrogen gas based on the manufacturing method of a material. For example, SiN etc. used as a material of a passivation film may contain ammonia gas based on the manufacturing method. For this reason, hydrogen gas generated by decomposition of ammonia from SiN may generate | occur | produce.

As described above, in electronic devices such as organic EL devices, members such as TFTs and metal wirings may be adversely affected by generation of hydrogen inside.

From such a problem, for example, the method of including a metal thin film as a hydrogen absorbing substance in an organic electroluminescent element (organic EL element) is proposed (refer patent document 1).

Japanese Patent Application Laid-Open No. 2015-79755

However, the method described in Patent Literature 1 is difficult to apply to a place where transparency is required, and a process including a hydrogen absorbing substance is added to the manufacturing method of the electronic device, and the manufacturing process of the electronic device becomes complicated. It becomes a factor of the increase in the manufacturing cost of the electronic device.

For this reason, by combining with the functional layer originally provided by an electronic element, the hydrogen barrier agent which can give a hydrogen barrier property to a functional layer, and the hydrogen barrier film formed using the said hydrogen barrier agent are calculated | required.

This invention is made | formed in view of the said subject, The composition for forming a hydrogen barrier film | membrane containing the hydrogen barrier agent which can give hydrogen barrier performance to various materials, and the said hydrogen barrier agent, and the above-mentioned hydrogen barrier agent It is an object of the present invention to provide an electronic device comprising a hydrogen barrier film, a method for producing a hydrogen barrier film using the above-described composition for forming a hydrogen barrier film, and a hydrogen barrier film.

MEANS TO SOLVE THE PROBLEM This inventor uses the salt compound of the specific structure which has imidazolyl group as a hydrogen barrier agent, mix | blended the above-mentioned hydrogen barrier agent with a base component, prepares the composition for hydrogen barrier film formation, and forms the hydrogen barrier film mentioned above. By forming a hydrogen barrier film using the composition for, it discovered that the said subject can be solved and came to complete this invention. Specifically, the present invention provides the following.

In addition, the "hydrogen" as the object of "hydrogen barrier" performance of the present invention is, refers to both whole both mixing components consisting of various elements and combinations of the individual components of the H ₂ molecule, H radical, H ^{+ (proton)} .

The 1st aspect of this invention is following formula (1):

[Formula 1]

(In formula (1), X ^{m <+>} represents a m-valent counter cation, R <^1> represents the aromatic group which may have a substituent, R <^2> represents the alkylene group which may have a substituent, R <^3> represents a halogen atom, a hydroxyl group, Mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfonic acid ester group, phosphino group, phosphinyl group, phosphonic acid ester group or organic group, m represents an integer of 1 or more, n is An integer of 0 or more and 3 or less, and R ² may be bonded to R ¹ to form a cyclic structure.)

It is a hydrogen barrier agent which consists of a compound represented by these.

The 2nd aspect of this invention is a composition for hydrogen barrier film formation containing a base material component (A) and the hydrogen barrier agent (B) which concerns on a 1st aspect.

A third aspect of the present invention is a hydrogen barrier film containing a hydrogen barrier agent according to the first aspect.

The 4th aspect of this invention is a composition for hydrogen barrier film formation which concerns on a 2nd aspect, Comprising: A base material component (A) contains alkali-soluble resin (A1) and a photopolymerizable compound (A2), The photoinitiator further It is a hydrogen barrier film which consists of hardened | cured material of the composition for hydrogen barrier film formation containing (C).

The fifth aspect of the present invention,

A hydrogen barrier film-forming composition according to a second aspect, wherein the base component (A) contains an alkali-soluble resin (A1) and a photopolymerizable compound (A2), and further includes a photopolymerization initiator (C). Forming a coating film by applying the film forming composition onto a substrate;

It is a manufacturing method of a hydrogen barrier film containing exposing a coating film.

A sixth aspect of the present invention is an electronic device including a passivation film and a hydrogen barrier film according to the third or fourth aspect.

According to the present invention, a hydrogen barrier agent capable of imparting hydrogen barrier performance to various materials, a composition for forming a hydrogen barrier film containing the hydrogen barrier agent, a hydrogen barrier film containing the above-described hydrogen barrier agent, The manufacturing method of the hydrogen barrier film using the composition for hydrogen barrier film formation mentioned above, and the electronic element provided with a hydrogen barrier film can be provided.

<Hydrogen barrier agent>

The hydrogen barrier agent consists of a compound represented by following formula (1). The hydrogen barrier agent is blended with various materials to impart hydrogen barrier properties to various articles.

[Formula 2]

(In formula (1), X ^{m <+>} represents a m-valent counter cation, R <^1> represents the aromatic group which may have a substituent, R <^2> represents the alkylene group which may have a substituent, R <^3> represents a halogen atom, a hydroxyl group, Mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfonic acid ester group, phosphino group, phosphinyl group, phosphonic acid ester group or organic group, m represents an integer of 1 or more, n is An integer of 0 or more and 3 or less, and R ² may be bonded to R ¹ to form a cyclic structure.)

It is preferable that m-valent counter cation X < ^{m +>} is acyclic or cyclic nitrogen-containing aliphatic cation, nitrogen-containing aromatic cation, or metal cation. It is preferable that m is an integer of 1 or more and 3 or less, 1 or 2 is more preferable, and 1 is more preferable.

As said cyclic nitrogen-containing aliphatic cation, hetero atoms (for example, oxygen atom, sulfur atom, etc.) other than a nitrogen atom may be included as an atom which comprises a ring.

As said acyclic or cyclic nitrogen-containing aliphatic cation, the cation represented by either of following formula (2)-(4) is preferable.

[Formula 3]

(In formula (2), R ¹¹ to R ¹⁴ are each independently a hydrogen atom, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, The aryl group which may have a substituent, the aralkyl group which may have a substituent, or the heterocyclic group which may have a substituent may be shown, and at least 2 selected from R <^11> -R <^14> may connect and form the ring.)

In Formula (2), as an alkyl group which may have a substituent, an alkyl group having 1 to 30 carbon atoms is preferable. As a specific example of the alkyl group which may have a substituent, a methyl group, an ethyl group, n-propyl group, n-butyl group, n-hexyl group, n-octyl group, n-decyl group, n-dodecyl group, n-octade Real group, isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, 1-ethylpentyl group, trifluoromethyl group, 2-ethylhexyl group, phenacyl group, 1-naphthoylmethyl group, 2-naphthoyl Methyl group, 4-methylsulfanyl phenacyl group, 4-phenylsulfanyl phenacyl group, 4-dimethylamino phenacyl group, 4-cyano phenacyl group, 4-methyl phenacyl group, 2-methyl phenacyl group, 3-fluoro phenacyl group , 3-trifluoromethylphenacyl group, 3-nitrophenacyl group, and the like.

As a cycloalkyl group which may have a substituent, the cycloalkyl group of 5 to 30 carbon atoms is preferable. As a specific example of the cycloalkyl group which may have a substituent, a cyclopentyl group, a cyclohexyl group, etc. are mentioned.

As an alkenyl group which may have a substituent, the alkenyl group of 2 to 10 carbon atoms is preferable. As a specific example of the alkenyl group which may have a substituent, a vinyl group, an allyl group, a styryl group, etc. are mentioned.

As an alkynyl group which may have a substituent, C2-C10 alkynyl group is preferable. As an example of the alkynyl group which may have a substituent, an ethynyl group, a propynyl group, a propargyl group, etc. are mentioned.

As an aryl group which may have a substituent, the C6-C30 aryl group is preferable. As a specific example of the aryl group which may have a substituent, a phenyl group, a biphenyl group, 1-naphthyl group, 2-naphthyl group, 9- anthryl group, 9-phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group , 1-indenyl group, 2-azrenyl group, 9-fluorenyl group, terphenyl group, quarterphenyl group, o-tolyl group, m-tolyl group, p-tolyl group, xylyl group, o-cumenyl group, m- Cumenyl group, p-cumenyl group, mesityl group, pentarenyl group, vinaphthalenyl group, ternaphthalenyl group, quarter naphthalenyl group, heptarenyl group, biphenylenyl group, indaseyl group, fluoranthrenyl group, acenaph Thirenyl group, aceanthrylenyl group, phenenalenyl group, fluorenyl group, anthryl group, bianthracenyl group, teranthracenyl group, quarter anthracenyl group, anthraquinolyl group, phenanthryl group, triphenylenyl group, pyrene Neyl group, chrysenyl group, naphthacenyl group, preadenyl group, pisenyl group, perylenyl group, pentaphenyl group, pentasenyl group, tetraphenylenyl group, hexaphenyl group, hexasenyl group, ru Hexenyl group, a co-Ro group, and the like tree tilre naphthyl group, a heptadecyl group, a heptadecyl hexenyl group, and a pyran group Trail, Oh-Barre group.

As the aralkyl group which may have a substituent, an aralkyl group having 7 to 20 carbon atoms is preferable, and for example, a benzyl group, phenethyl group, α-naphthylmethyl group, β-naphthylmethyl group, and 2-α- A naphthyl ethyl group, 2- (beta) -naphthyl ethyl group, etc. are mentioned.

As a heterocyclic group which may have a substituent, the aromatic or aliphatic heterocyclic ring containing a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom is preferable. Specific examples of the heterocycle include thienyl group, benzo [b] thienyl group, naphtho [2,3-b] thienyl group, thianthrenyl group, furyl group, pyranyl group, isobenzofuranyl group, chromenyl group, x Santenyl group, phenoxatinyyl group, 2H-pyrrolyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyridinyl group, pyrimidinyl group, pyridadidinyl group, indolidinyl group, isoindolyl group, 3H -Indolyl group, indolyl group, 1H-indazolyl group, furinyl group, 4H-quinolidinyl group, isoquinolyl group, quinolyl group, phthaladilinyl group, naphthyridinyl group, quinoxanillyl group, quinazolinyl group, shin Nolinyl group, pterridinyl group, 4aH-carbazolyl group, carbazolyl group, β-carbolinyl group, phenanthryldinyl group, acridinyl group, perimidinyl group, phenanthrolinyl group, phenadidinyl group, phenarsadiyl Neyl group, isothiazolyl group, phenothiadinyl group, isoquisazolyl group, furazanyl group, phenoxadinyl group, isochromenyl group, chromanyl group, pyrrolidinyl Group, pyrrolidinyl group, imidazolidinyl group, imidazolinyl group, pyrazolidinyl group, pyrazolinyl group, piperidyl group, piperadinyl group, indolyl group, isoindolyl group, quinukridinyl group, morpholine And a thioxantholyl group.

Moreover, the alkyl group which may have a substituent mentioned above, the cycloalkyl group which may have a substituent, the alkenyl group which may have a substituent, the alkynyl group which may have a substituent, the aryl group which may have a substituent, and the aralkyl group which may have a substituent Or the hydrogen atom of the heterocyclic group which may have a substituent may be substituted by the other substituent further.

Such substituents include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; cyano group; nitro group; alkoxy group such as methoxy group, ethoxy group and tert-butoxy group; phenoxy group and p-tolyloxy group Aryloxy groups such as; acyloxy groups such as acetoxy group, propionyloxy group and benzoyloxy group; alkoxycarbonyl groups such as methoxycarbonyl group and butoxycarbonyl group; aryloxycarbonyl groups such as phenoxycarbonyl group; vinyloxycarbonyl group and allyl Alkenyloxycarbonyl groups, such as an oxycarbonyl group; Acyl groups, such as an acetyl group, a benzoyl group, isobutyryl group, acryloyl group, a methacryloyl group, and a methoxylyl group; Alkyl sulfanyl groups, such as a methyl sulfanyl group and tert- butyl sulfanyl group Arylsulfanyl groups such as phenylsulfanyl group and p-tolylsulfanyl group; aliphatic secondary amino groups such as methylamino group and cyclohexylamino group; Aliphatic tertiary amino groups, such as no group, diethylamino group, morpholino group, and piperidino group; aromatic secondary amino groups such as phenylamino group and p-tolylamino group; alkyl groups such as methyl group, ethyl group, tert-butyl group, and dodecyl group Aryl groups such as phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group and phenanthryl group; hydroxy group; carboxy group; sulfonamide group; formyl group; mercapto group; sulfo group; mesyl group; p-toluenesulfonyl group; primary amino group; nitroso group; halogenated alkyl groups such as trifluoromethyl group and trichloromethyl group; trimethylsilyl group; phosphinico group; phosphono group; alkylsulfonyl group; arylsulfonyl group; trialkyl An ammonium group, a dimethyl sulfonium group, a triphenyl phenacyl phosphonium group, etc. are mentioned.

In the formula (2), when at least two selected from R ¹¹ to R ¹⁴ are linked to form a ring, an alkylene group, a cycloalkylene group or a divalent group formed by connecting them can be mentioned as the linking group. As the linking group, a divalent group having 1 to 10 carbon atoms is preferable. The ring formed from at least two selected from R ¹¹ to R ¹⁴ may contain an oxygen atom as an atom constituting the ring.

(R ²¹ ) ₂ N ⁺ = C (NR ²² ₂ ) ₂ (3)

(Formula (3) of, R ²¹ each independently represents a hydrogen atom, an alkyl group or a cycloalkyl group, R ²² is independently a hydrogen atom, an alkyl group, a cycloalkyl group, -C (= NR ^23, respectively) -NR ²³ ₂ (3 R ²³ each independently represent a hydrogen atom, an alkyl group or a cycloalkyl group) or = C (-NR ²⁴ ₂ ) ₂ (four R ²⁴ each independently represent a hydrogen atom or an organic group).

As the alkyl group for R ²¹ to R ²³ , an alkyl group having 1 to 10 carbon atoms is preferable. Specific examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, octadecyl group, isopropyl group, isobutyl group, sec-butyl group and tert-butyl group And 1-ethylpentyl group.

As a cycloalkyl group for R <^21> -R <^23> , a cycloalkyl group of 5 or more carbon atoms is preferable. As a specific example of a cycloalkyl group, a cyclopentyl group, a cyclohexyl group, etc. are mentioned.

As an organic group with respect to R <^24> , an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, etc. are mentioned.

As a cation represented by Formula (3), 1, 2- diisopropyl-3- [bis (dimethylamino) methylene] guanidium, 1-methyl biguanium, 1-n-butyl biguanium, 1 -(2-ethylhexyl) biguanium, 1-n-octadecyl biguanium, 1,1-dimethyl biguanium, 1,1-diethyl biguanium, 1-cyclohexyl biguanium, 2-ethyl-1,1,3,3-tetramethylguanidium, 1-benzylguanidium, 1,3-dibenzylguanidium, 1-benzyl-2,3-dimethylguanidium, 1- Phenyl guanidium etc. are mentioned, A 1, 2- diisopropyl-3- [bis (dimethylamino) methylene] guanidium is preferable.

[Formula 4]

(In formula (4), R <^31> represents a hydrogen atom or an organic group each independently, and s represents the integer of 2 or more and 6 or less.)

As an organic group with respect to R <^31> , an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, etc. are mentioned. The alkyl group, the cycloalkyl group, the aralkyl group and the aryl group may have a substituent. Examples of the substituent include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; cyano group; nitro group; alkoxy group such as methoxy group, ethoxy group and tert-butoxy group; phenoxy group and p-tolyloxy group Aryloxy groups such as; acyloxy groups such as acetoxy group, propionyloxy group and benzoyloxy group; alkoxycarbonyl groups such as methoxycarbonyl group and butoxycarbonyl group; aryloxycarbonyl groups such as phenoxycarbonyl group; vinyloxycarbonyl group and allyl Alkenyloxycarbonyl groups, such as an oxycarbonyl group; Acyl groups, such as an acetyl group, a benzoyl group, isobutyryl group, acryloyl group, a methacryloyl group, and a methoxylyl group; Alkyl sulfanyl groups, such as a methyl sulfanyl group and tert- butyl sulfanyl group Arylsulfanyl groups such as phenylsulfanyl group and p-tolylsulfanyl group; aliphatic secondary amino groups such as methylamino group and cyclohexylamino group; dimethylami Aliphatic tertiary amino groups such as groups, diethylamino groups, morpholino groups and piperidino groups; aromatic secondary amino groups such as phenylamino groups and p-tolylamino groups; alkyl groups such as methyl groups, ethyl groups, tert-butyl groups and dodecyl groups Aryl groups such as phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group and phenanthryl group; hydroxy group; carboxy group; sulfonamide group; formyl group; mercapto group; sulfo group; mesyl group; p-toluenesulfonyl group; primary amino group; nitroso group; halogenated alkyl groups such as trifluoromethyl group and trichloromethyl group; trimethylsilyl group; phosphinico group; phosphono group; alkylsulfonyl group; arylsulfonyl group; trialkyl An ammonium group, a dimethyl sulfonium group, a triphenyl phenacyl phosphonium group, etc. are mentioned.

It is preferable that it is an integer of 3 or more and 5 or less, and, as for s, it is more preferable that it is 3 or 4.

It is preferable that it is a cation containing an aromatic group with respect to counter cation X ^m . It is preferable that the aromatic group contained in counter cation X ^m is an aromatic heterocyclic group. It is preferable that the aromatic group contained in counter cation X ^m is a nitrogen-containing aromatic heterocyclic group. As a nitrogen-containing aromatic cation with respect to counter cation X ^{m +} , the cation represented by either of following formula (5)-(13) is preferable.

[Formula 5]

(Wherein, R ^H each independently represents a hydrogen atom or an alkyl group. R ⁴¹ , R ⁴³ , R ⁴⁵ , R ⁴⁶ , R ⁴⁷ , R ⁴⁸ , R ⁵⁰ , R ⁵¹ and R ⁵² each independently represent a hydrogen atom, R ⁴² , R ⁴⁴ and R ⁴⁹ each independently represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group or an alkynyl group, and a halogen group, a cyano group, a nitro group, an alkyl group, a cycloalkyl group, an alkenyl group or an alkynyl group. R ⁴¹ to R ⁵² may be each independently substituted with a halogen atom, a cyano group or a nitro group.

R ⁴¹ and R ⁴² may be bonded to each other to form a ring. At least two R ⁴¹ may be bonded to each other to form a ring. R ⁴³ and R ⁴⁴ may be bonded to each other to form a ring. Two R ^{43 's} may be bonded to each other to form a ring. At least two R ^{45 's} may be bonded to each other to form a ring. At least two R ⁴⁶ may be bonded to each other to form a ring. At least two R ⁴⁷ may be bonded to each other to form a ring. R ⁴⁸ and R ⁴⁹ may be bonded to each other to form a ring. At least two R ^{48 's} may be bonded to each other to form a ring. At least two R ^{50 's} may be bonded to each other to form a ring. At least two R ^{51 's} may be bonded to each other to form a ring. At least two R ⁵² may be bonded to each other to form a ring.)

^Examples of the halogen atom for R ⁴¹ to R ⁵² include a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

The alkyl group for R ^H and R ⁴¹ to R ⁵² may be a straight chain alkyl group or a branched chain alkyl group. The number of carbon atoms of the alkyl group is not particularly limited. 1 or more and 20 or less are preferable, as for carbon number of an alkyl group, 1 or more and 10 or less are more preferable, and 1 or more and 5 or less are especially preferable.

Specific examples of the alkyl group for R ^H and R ⁴¹ to R ⁵² include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n -Pentyl group, isopentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethyl-n-hexyl group, n-nonyl group, n-decyl group, n-unde Real group, n-dodecyl group, n-tridecyl group, n- tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, and n -An etheryl group.

As a cycloalkyl group for R ⁴¹ to R ⁵² , a cycloalkyl group having 5 to 30 carbon atoms is preferable. As a specific example of a cycloalkyl group, a cyclopentyl group, a cyclohexyl group, etc. are mentioned.

As the alkenyl group for R ⁴¹ to R ⁵² , an alkenyl group having 2 to 10 carbon atoms is preferable. As a specific example of an alkenyl group, a vinyl group, an allyl group, a styryl group, etc. are mentioned.

As the alkynyl group for R ⁴¹ to R ⁵² , an alkynyl group having 2 to 10 carbon atoms is preferable. As an example of an alkynyl group, an ethynyl group, a propynyl group, a propargyl group, etc. are mentioned.

When m is an integer greater than or equal to 2, it is preferable that it is represented by either of following formula (14)-(16) as acyclic or cyclic nitrogen-containing aliphatic cation with respect to mvalent counter cation Xm ⁺ .

[Formula 6]

(In the formula, R ^H each independently represents a hydrogen atom or an alkyl group. R ⁵³ and R ⁵⁵ each independently represent an alkyl group or a cycloalkyl group. R ⁵⁴ represents an alkylene group, a cycloalkylene group, or 2 formed by linking them. R ⁵⁶ represents an alkylene group R ⁵³ to R ⁵⁶ may be each independently substituted with a halogen atom, a cyano group or a nitro group, and at least two R ⁵³ may be bonded to each other to form a ring. R ⁵³ and R ⁵⁴ may be bonded to each other to form a ring. Two R ⁵⁵ may be bonded to each other to form a ring.)

Specific examples and preferable examples of R ^H include the same ones as the specific examples and preferred examples described above.

Examples of the alkyl group for R ^H and R ⁵³ to R ⁵⁵ include the same alkyl groups as the specific examples and preferred examples described above as the alkyl group for R ^H and R ⁴¹ to R ⁵² .

Examples of the cycloalkyl group for R ⁵³ to R ⁵⁵ include the same cycloalkyl group as the specific examples and preferred examples described above as the cycloalkyl group for R ⁴¹ to R ⁵² .

^Examples of the alkylene group for R ⁵⁶ include an alkylene group having 1 to 5 carbon atoms. As a specific example of an alkylene group, a methylene group, ethylene group, a propylene group, butylene group, etc. are mentioned.

When m is an integer greater than or equal to 2, as a nitrogen-containing aromatic cation with respect to mvalent counter cation X ^{m +} , a 2, 2- bipyridinium skeleton, a 3, 3- bipyridinium skeleton, a 4, 4- bipyridinium skeleton in a molecule | numerator , 2,2-bipyridinium skeleton, 4,4-biquinolinium skeleton, 4,4-biisoquinolinium skeleton, 4- [2- (4-pyridinium) vinyl] pyridinium skeleton or 4- [ And divalent or higher cations having a 4- (4-pyridinium) phenyl] pyridinium skeleton.

The metal cation for the counter cation X ^{m +} is preferably a cation of a metal atom selected from the group consisting of a typical metal element, a transition metal element and a semimetal element, or a cation of an atomic group containing the metal atom.

Examples of the typical metal element include an alkali metal element (a metal element consisting of elements other than hydrogen in the periodic table group 1, for example, sodium and potassium), an alkaline earth metal element (metal element composed of an element of the periodic table group 2, For example, magnesium), a metal element (for example, zinc) composed of elements of group 12 of the periodic table, a metal element (for example, aluminum) composed of elements other than boron in the group 13 of the periodic table, group 14 Metallic elements (for example, tin) consisting of elements other than heavy carbon and silicon, metallic elements (for example antimony) consisting of elements other than nitrogen, phosphorus and arsenic in group 15 of the periodic table, oxygen in group 16 A metal element (for example, polonium) which consists of elements except sulfur, selenium, and terrules is mentioned.

As said transition metal element, the metal element (for example, hafnium) which consists of elements of group 3-11 of the periodic table is mentioned.

Examples of the semimetal element include boron, silicon, arsenic, selenium, and terul.

As a cation of the atomic group containing the said metal atom, the atomic group etc. containing both a metal atom and a nonmetal atom are mentioned. Specifically, [ZrO] ²⁺ , [(C ₂ H ₅ O) Al] ²⁺ , [(nC ₄ H ₉ ) ₂ Sn—O—Sn (nC ₄ H ₉ ) ₂ ] ²⁺ , and the like.

In formula (1), R <^1> represents the aromatic group which may have a substituent. The aromatic group which may have a substituent may be the aromatic hydrocarbon group which may have a substituent, or the aromatic heterocyclic group which may have a substituent may be sufficient as it.

The kind of aromatic hydrocarbon group is not specifically limited in the range which does not impair the objective of this invention. The aromatic hydrocarbon group may be a monocyclic aromatic group, may be formed by condensation of two or more aromatic hydrocarbon groups, or may be formed by bonding two or more aromatic hydrocarbon groups by a single bond. As an aromatic hydrocarbon group, a phenyl group, a naphthyl group, a biphenylyl group, an anthryl group, and a phenanthrenyl group are preferable.

The kind of aromatic heterocyclic group is not specifically limited in the range which does not impair the objective of this invention. The aromatic heterocyclic group may be a monocyclic group or a polycyclic group. Examples of the aromatic heterocyclic group include a pyridyl group, a furyl group, a thienyl group, an imidazolyl group, a pyrazolyl group, an oxazolyl group, a thiazolyl group, an isoxazolyl group, an isothiazolyl group, a benzoxazolyl group, a benzothiazolyl group and Benzimidazolyl groups are preferred.

As a substituent which a phenyl group, a polycyclic aromatic hydrocarbon group, or an aromatic heterocyclic group may have, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfino group, a sulfo group, a sulfonic acid ester A group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonic acid ester group, an amino group, an ammonia group, and an organic group are mentioned. When a phenyl group, a polycyclic aromatic hydrocarbon group, or an aromatic heterocyclic group has a some substituent, the said some substituent may be same or different.

When the substituent which an aromatic group has is an organic group, an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, an aralkyl group, etc. are mentioned as said organic group. This organic group may contain the bond and substituents other than hydrocarbon groups, such as a hetero atom, in the said organic group. The organic group may be any of linear, branched, and cyclic. Although this organic group is monovalent normally, when forming a cyclic structure, it can become a divalent or more organic group.

When an aromatic group has a substituent on the adjacent carbon atom, the two substituents couple | bonded on the adjacent carbon atom may combine with it, and may form cyclic structure. Examples of the cyclic structure include aliphatic hydrocarbon rings and aliphatic rings containing hetero atoms.

When the substituent which an aromatic group has is an organic group, the bond contained in the said organic group is not specifically limited, unless the effect of this invention is impaired, The organic group is a bond containing hetero atoms, such as an oxygen atom, a nitrogen atom, and a silicon atom It may include. As a specific example of the bond containing a hetero atom, an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, an ester bond, an amide bond, an amino bond (-NR ^A- : R ^A is a hydrogen atom or monovalent Organic group) urethane bond, imino bond (-N = C (-R ^B )-, -C (= NR ^B )-: R ^B represents a hydrogen atom or monovalent organic group), carbonate bond, sulfonyl bond , Sulfinyl bonds, azo bonds and the like.

As a bond containing the hetero atom which an organic group may have, it is an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, an ester bond, an amide from a heat resistant viewpoint of the imidazole compound represented by Formula (1). Bond, amino bond (-NR ^A- : R ^A represents a hydrogen atom or monovalent organic group) Urethane bond, imino bond (-N = C (-R ^B )-, -C (= NR ^B )-: R ^B represents a hydrogen atom or a monovalent organic group), a carbonate bond, a sulfonyl bond, and a sulfinyl bond is preferable.

When an organic group is a substituent other than a hydrocarbon group, the kind of substituents other than a hydrocarbon group is not specifically limited in the range which does not impair the objective of this invention. As a specific example of substituents other than a hydrocarbon group, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a cyano group, an isocyano group, a cyanate group, an isocyanate group, a thiocyanate group, an isothiocyanate group, a silyl group, Silanol group, alkoxy group, alkoxycarbonyl group, amino group, monoalkylamino group, dialkylamino group, monoarylamino group, diarylamino group, carbamoyl group, thiocarbamoyl group, nitro group, nitroso group, carboxylate group, acyl group, Acyloxy group, sulfino group, sulfonic acid ester group, phosphino group, phosphinyl group, phosphonic acid ester group, alkyl ether group, alkenylether group, alkylthioether group, alkenylthioether group, arylether group and aryl A thioether group etc. are mentioned. The hydrogen atom contained in the said substituent may be substituted by the hydrocarbon group. Moreover, any of linear, branched, and cyclic | annular may be sufficient as the hydrocarbon group contained in the said substituent.

As a substituent which a phenyl group, a polycyclic aromatic hydrocarbon group, or an aromatic heterocyclic group has, C1-C12 alkyl group, C1-C12 aryl group, C1-C12 alkoxy group, C2-C atom 1 or more and 12 or less aryloxy groups, C1 or more and 12 or less arylamino groups and halogen atoms are preferable.

As R ¹ , the compound represented by the formula (1) can be synthesized at low cost and easily, and since the solubility in water and the organic solvent of the compound is good, a phenyl group, a furyl group, and thienyl may each have a substituent. Groups are preferred.

In formula (1), R <^2> is the alkylene group which may have a substituent. The substituent which the alkylene group may have is not specifically limited in the range which does not impair the objective of this invention. As a specific example of the substituent which the alkylene group may have, a hydroxyl group, an alkoxy group, an amino group, a cyano group, a halogen atom, etc. are mentioned. The alkylene group may be a linear alkylene group or a branched alkylene group, and a linear alkylene group is preferable. Although the number of carbon atoms of an alkylene group is not specifically limited, 1 or more and 20 or less are preferable, 1 or more and 10 or less are preferable, and 1 or more and 5 or less are more preferable. In addition, the carbon atom number of an alkylene group does not contain the carbon atom of the substituent couple | bonded with an alkylene group.

The alkoxy group as a substituent bonded to the alkylene group may be a straight chain alkoxy group or a branched chain alkoxy group. Although the number of carbon atoms of the alkoxy group as a substituent is not specifically limited, 1 or more and 10 or less are preferable, 1 or more and 6 or less are more preferable, 1 or more and 3 or less are especially preferable.

The amino group as a substituent bonded to the alkylene group may be a monoalkylamino group or a dialkylamino group. The alkyl group contained in a monoalkylamino group or a dialkylamino group may be a linear alkyl group or a branched alkyl group. Although the number of carbon atoms of the alkyl group contained in a monoalkylamino group or a dialkylamino group is not specifically limited, 1 or more and 10 or less are preferable, 1 or more and 6 or less are more preferable, 1 or more and 3 or less are especially preferable.

Specific examples of the alkylene group suitable as R ² include methylene group, ethane-1,2-diyl group, n-propane-1,3-diyl group, n-propane-2,2-diyl group, n-butane- 1,4-diyl group, n-pentane-1,5-diyl group, n-hexane-1,6-diyl group, n-heptane-1,7-diyl group, n-octane-1,8-diyl group , n-nonane-1,9-diyl group, n-decane-1,10-diyl group, n-undecane-1,11-diyl group, n-dodecane-1,12-diyl group, n-tree Decane-1,13-diyl group, n-tetradecane-1,14-diyl group, n-pentadecane-1,15-diyl group, n-hexadecane-1,16-diyl group, n-heptadecane- And 1,17-diyl groups, n-octadecane-1,18-diyl groups, n-nonadecan-1,19-diyl groups and n-icoic acid-1,20-diyl groups.

R ³ is a halogen atom, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfonic acid ester group, phosphino group, phosphinyl group, phosphonic acid ester group or organic group. n is an integer of 0 or more and 3 or less. When n is an integer of 2 or more and 3 or less, some R <^3> may be same or different, respectively.

When R <^3> is an organic group, the said organic group is the same as the organic group which the aromatic group may have as a substituent with respect to R <^1> .

When R <^3> is an organic group, as an organic group, an alkyl group, an aromatic hydrocarbon group, and an aromatic heterocyclic group are preferable. As an alkyl group, a C1-C8 linear or branched alkyl group is preferable, and a methyl group, an ethyl group, n-propyl group, and isopropyl group are more preferable. As an aromatic hydrocarbon group, a phenyl group, a naphthyl group, a biphenylyl group, an anthryl group, and a phenanthrenyl group are preferable, a phenyl group and a naphthyl group are more preferable, and a phenyl group is especially preferable. As an aromatic heterocyclic group, a pyridyl group, a furyl group, thienyl group, imidazolyl group, pyrazolyl group, oxazolyl group, thiazolyl group, isoxazolyl group, isothiazolyl group, benzoxazolyl group, benzothiazoleyl group And a benzimidazolyl group are preferable, and a furyl group and thienyl group are more preferable.

When R <^3> is an alkyl group, the bonding position of the alkyl group on the imidazole ring may be any of 2-position, 4-position, and 5-position, and 2-position is more preferable. When R <^3> is an aromatic hydrocarbon group and an aromatic heterocyclic group, the coupling | positioning position on the imidazole of these groups has preferable 2-position.

Among the compounds represented by the above formula (1), compounds represented by the following formula (1-1) are preferable because of the low cost and easy synthesis, and excellent solubility in water and an organic solvent, More preferable are compounds represented by 1-1) and R ² is a methylene group.

[Formula 7]

(In formula (1-1), X, R <^2> , R <^3> , m and n are synonymous with Formula (1), and R <^4> , R <^5> , R <^6> , R <^7> and R <^8> are respectively independently hydrogen. Atom, halogen atom, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino group, sulfo group, sulfonic acid ester group, phosphino group, phosphinyl group, phosphono group, phosph an acid ester group, an amino group, comes ammonia or an organic group, with the proviso that, R ^4, R ^5, R ^6, R ⁷ and R at least one of the ⁸ is a group other than a hydrogen atom. R ^4, R ^5, R ^6, R At least two of ⁷ and R ⁸ may be bonded to each other to form a cyclic structure, and R ² may be bonded to R ⁶ to form a cyclic structure.)

When R <^4> , R <^5> , R <^6> , R <^7> and R <^8> are organic groups, the said organic group is the same as the organic group which R <^1> in Formula (1) has as a substituent. It is preferable that R <^4> , R <^5> , R <^6> and R <^7> are hydrogen atoms from the point of the solubility with respect to the solvent of the said compound.

Especially, it is preferable that at least one of R <^4> , R <^5> , R <^6> , R <^7> and R <^8> is the following substituent, and it is especially preferable that R <^8> is the following substituent. When R <^8> is the following substituent, it is preferable that R <^4> , R <^5> , R <^6> and R <^7> are hydrogen atoms.

-OR ⁹

(R ⁹ is a hydrogen atom or an organic group.)

When R <^9> is an organic group, the said organic group is the same as the organic group which R <^1> in Formula (1) has as a substituent. As R ⁹ , an alkyl group is preferable, an alkyl group having 1 to 8 carbon atoms is more preferable, an alkyl group having 1 to 3 carbon atoms is particularly preferable, and a methyl group is most preferred.

In the compound represented by the said Formula (1-1), the compound represented by following formula (1-1-1) is preferable.

[Formula 8]

In (formula ^{(1-1-1), X, R 3} , R 4, R 5, R 6, R 7 and R ^8, m and n ^{are, R 4, R 5, R} 6, R 7 and R At least one of ⁸ is the same meaning as Formula (1) except having a group other than a hydrogen atom.

Among the compounds represented by the formula (1-1-1), at least one of R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ is preferably a group represented by -OR ⁹ described above, and R ⁸ is -OR ^9. It is especially preferable that it is group represented by. When R <^8> is group represented by -OR <^9> , it is preferable that R <^4> , R <^5> , R <^6> and R <^7> are hydrogen atoms.

As a suitable specific example of a compound represented by Formula (1), the following are mentioned.

[Formula 9]

[Formula 10]

[Formula 11]

(Method for Producing Compound Represented by Formula (1))

There is no restriction | limiting in particular as a manufacturing method of the compound represented by said Formula (1). For example, the compound represented by said formula (1) can be manufactured by neutralizing-reacting the compound represented by following formula (10) with the base which can form the counter value of cation ^{Xm <+>} in a solvent or a nonsolvent. .

[Formula 12]

(In Formula (10), R <^1> , R <^2> , R <^3> and n are synonymous with Formula (1), and a specific example and a preferable example are also the same.)

As a base which can form mvalent counter cation X ^{m +} , it is preferable that it is an acyclic or cyclic nitrogen-containing aliphatic compound, a nitrogen-containing aromatic compound, a metal atom, or the atomic group containing the said metal atom.

As a base which can form mvalent counter cation X < ^{m +>} , the acyclic or cyclic nitrogen-containing aliphatic cation represented by any one of said Formula (2)-(4), any of said Formula (5)-(13) A nitrogen-containing aromatic cation represented by one, a nitrogen-containing aliphatic cation represented by any one of the formulas (14) to (16), or a cation of a metal atom selected from the group consisting of typical metal elements, transition metal elements and semimetal elements, or It is more preferable that it is a base which can form the cation of the atomic group containing the said metal atom.

As a method for neutralizing the compound represented by the formula (10) and the base in a solvent, under heating or non-heating, for example, the compound represented by the formula (10) and the base in a polar solvent The method of mixing, etc. are mentioned.

Alcohol is mentioned as said polar solvent. Specifically, methanol, ethanol, propanol, isopropanol, butanol, t-butanol, etc. are mentioned.

Under heating (for example, 40 ° C. or higher, preferably 50 ° C. or higher, more preferably 55 ° C. or higher), the compound represented by Formula (10) and the base may be dissolved in the solvent and mixed. .

Although there is no restriction | limiting in particular as an upper limit of the temperature at the time of heating, It is preferable that it is below the boiling point of the said solvent.

Even if the compound represented by the formula (10) or the base is difficult to dissolve in the solvent under unheating, solubility in the solvent may also proceed as the neutralization reaction and salt formation proceed.

As a method for neutralizing the compound represented by the formula (10) and the base in a non-solvent, for example, the base represented by the compound represented by the formula (10) which is a solid at room temperature and the base which is a solid or a liquid is induced. Pulverizing or crushing, etc., and mixing.

Moreover, there is no restriction | limiting in particular as ratio (molar ratio) of the compound represented by the said Formula (10), The said base which makes mole number of the compound represented by Formula (10) M1, and gives m valent counter cation ^{Xm +} . When the number of moles of the base is M2, the value of M1 / (M2 / m) is preferably 20/80 to 80/20, more preferably 30/70 to 70/30.

In addition, the compound represented by the formula (1) wherein X ^{m +} is a sodium cation or a potassium cation and a base capable of forming a relative cation X ^{m +} other than the sodium cation and the potassium cation are mixed with each other to perform salt exchange. ^{m +} can also manufacture the compound represented by said Formula (1) other than a sodium cation and a potassium cation.

`` Composition for hydrogen barrier film formation ''

The composition for hydrogen barrier film formation contains a base material component (A) and the above-mentioned hydrogen barrier agent (B). Hereinafter, the component which can be contained in the composition for hydrogen barrier film formation, and the composition suitable as a composition for hydrogen barrier film formation are demonstrated.

<Base material component (A)>

The base material component (A) is formed into a composition for forming a hydrogen barrier film by a film forming property capable of producing a film of a desired shape by a known method such as a melt processing method, or by a treatment such as exposure, heating, or reaction with water. It is a component which gives the film forming property which can manufacture a film.

A base material component (A) will not be specifically limited if it is a material which can provide desired film forming property to the composition for hydrogen barrier film formation.

As the base material component (A), a thermosetting resin which is cured by typically producing a high molecular compound by crosslinking by heating with a resin material made of a high molecular compound or by heating, or by chemical modification such as intramolecular cyclization by heating. The photopolymerizable compound which can be hardened by a material, exposure, the hydrolysis-condensable silane compound hydrolyzed and condensed by moisture in a composition, or an atmosphere, etc. are used.

Examples of the hydrolytic condensable silane compound include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, phenyltrimethoxysilane, And alkoxysilane compounds such as phenyltriethoxysilane, dimethyldimethoxysilane, diethyldimethoxysilane, dimethyldiethoxysilane, diethyldiethoxysilane, diphenyldimethoxysilane and diphenyldiethoxysilane. The hydrolysis-condensable silane compound may be a partial hydrolysis-condensation product of these silane compounds.

[Resin material]

In the base material component (A), examples of the resin material include polyacetal resin, polyamide resin, polycarbonate resin, polyester resin (polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polyarylate, etc.), FR -AS resin, FR-ABS resin, AS resin, ABS resin, polyphenylene oxide resin, polyphenylene sulfide resin, polysulfone resin, polyether sulfone resin, polyether ether ketone resin, fluorine resin, polyimide resin, poly Amideimide resin, polyamidebismaleimide resin, polyetherimide resin, polybenzoxazole resin, polybenzothiazole resin, polybenzoimidazole resin, silicone resin, BT resin, polymethylpentene, ultra high molecular weight polyethylene, FR- Polypropylene, (meth) acrylic resin (for example, polymethyl methacrylate etc.), polystyrene, etc. are mentioned.

When using a resin material as a base material component (A), in a resin material, the hydrogen barrier film | membrane is formed by film-forming the resin material in which the above-mentioned hydrogen barrier agent (B) was mix | blended by employing a desired method from the conventionally known film forming method. Are manufactured.

As a film forming method, melt processing methods, such as a T-die method (cast method), an inflation method, a press method, the casting method using a solution, etc. are mentioned.

In the cast method, a solution containing a resin material and a hydrogen barrier agent (B) is applied or cast on a substrate to form a film made of a solution, and then the solvent is removed from the film by a method such as heating to obtain hydrogen. A barrier film is formed.

The hydrogen barrier film obtained using the resin material may be subjected to stretching treatment such as uniaxial stretching or biaxial stretching as necessary.

When using the said resin material as a base material component (A), even if the composition for hydrogen barrier film formation contains additives and reinforcement materials, such as antioxidant, a ultraviolet absorber, a flame retardant, a mold release agent, a plasticizer, a filler, and a reinforcing material, as needed. do.

Moreover, when the composition for hydrogen barrier film formation is a composition for casting, the composition for hydrogen barrier film formation may contain the solvent. The kind of solvent is suitably selected according to the kind of resin material.

When the composition for hydrogen barrier film formation contains the said resin material and a hydrogen barrier agent (B), content of a hydrogen barrier agent is 0.01 mass% or more and 30 mass with respect to the mass of the resin material of the composition for hydrogen barrier film formation. % Or less is preferable, 0.05 mass% or more and 20 mass% or less are more preferable, 0.1 mass% or more and 10 mass% or less are especially preferable.

Thermosetting Material

As a thermosetting material, the precursor material of various thermosetting resins conventionally used widely is mentioned. Specific examples of the thermosetting resin include phenol resins, epoxy resins, oxetane resins, melamine resins, urea resins, unsaturated polyester resins, alkyd resins, polyurethane resins, polyimide resins, polybenzoxazole resins, and polybenzoimidazoles. Resin and the like.

Moreover, the resin which produces | generates the aromatic ring formation reaction in a molecule | numerator, and / or the crosslinking reaction between molecules by heating, is also used suitably as a thermosetting material. Hereinafter, resin which produces the aromatic ring formation reaction in a molecule | numerator, and / or the crosslinking reaction between molecules by heating is also called precursor resin.

Among these, epoxy resin precursors and precursor resins are particularly preferable because hydrogen barrier films having excellent heat resistance, chemical resistance, mechanical properties, and the like are particularly easy to be formed.

Hereinafter, the precursor material which is particularly suitable as the substrate component (A) will be described with respect to the thermosetting material.

(Epoxy resin precursor)

As an epoxy resin precursor, various epoxy compounds conventionally widely known can be used. The molecular weight of such an epoxy compound is not specifically limited. Among the epoxy compounds, a polyfunctional epoxy compound having two or more epoxy groups in the molecule is preferable because it is easy to form a hydrogen barrier film having excellent heat resistance, chemical resistance, mechanical properties, and the like. An epoxy resin precursor can be used individually or in combination of 2 or more types.

The polyfunctional epoxy compound is not particularly limited as long as it is a bifunctional or higher epoxy compound. Examples of the polyfunctional epoxy compound include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bisphenol AD type epoxy resins, naphthalene type epoxy resins, tetrabromine bisphenol A type epoxy resins, and biphenyl type epoxy resins. Bifunctional epoxy resins such as; Glycidyl ester epoxy resins such as dimer acid glycidyl ester and triglycidyl ester; Glycidylamine type epoxy resins such as tetraglycidylaminodiphenylmethane, triglycidyl-p-aminophenol, tetraglycidyl methacrylylenediamine and tetraglycidylbisaminomethylcyclohexane; Hydane-type epoxy resins, such as 1, 3- diglycidyl-5-methyl-5-ethyl hydanthine; Hydroquinone type epoxy resins; Fluorene type epoxy resins; Heterocyclic epoxy, such as triglycidyl isocyanurate Suzy; Fluoroglycinol triglycidyl ether, trihydroxybiphenyltriglycidyl ether, trihydroxyphenylmethanetriglycidyl ether, glycerin triglycidyl ether, 2- [4- (2,3-epoxypropoxy) Phenyl] -2- [4- [1,1-bis [4- (2,3-epoxypropoxy) phenyl] ethyl] phenyl] propane and 1,3-bis [4- [1- [4- (2 , 3-epoxypropoxy) phenyl] -1- [4- [1- [4- (2,3-epoxypropoxy) phenyl] -1-methylethyl] phenyl] ethyl] phenoxy] -2-propanol and the like Trifunctional epoxy resins; And tetrafunctional epoxy resins such as tetrahydroxyphenyl ethane tetraglycidyl ether, tetraglycidyl benzophenone, bis resorcinol tetraglycidyl ether, and tetraglycidoxy biphenyl. These epoxy compounds may be halogenated and may be hydrogenated.

As a commercially available polyfunctional epoxy compound, JER coat 828, 1001, 801N, 806, 807, 152, 604, 630, 871, YX8000, YX8034, YX4000 made by Japan epoxy resin company, for example, is made by DIC Corporation. Crow 830, EXA835LV, HP4032D, HP820, EP4100 series, EP4000 series, EPU series, Celoxide series (2021, 2021P, 2083, 2085, 3000, etc.) made by ADEKA Corporation, Eporide series, EHPE series, Shinil YD series, YDF series, YDCN series, YDB series, phenoxy resin (made from polyhydroxypolyether synthesized from bisphenols and epichlorohydrin; having epoxy group at the sock end; YP series, etc.), Nagase Chem Denacol series by Tex Corporation, the epolite series by Kyoeisha Chemical Co., Ltd., etc. are mentioned, It is not limited to these.

Moreover, an alicyclic epoxy compound is also preferable as a polyfunctional epoxy compound from the point which gives a hardened | cured material of high hardness. Specific examples of the alicyclic epoxy compound include 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-meta-dioxane and bis (3,4-epoxycyclohexyl Methyl) adipate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3 ', 4'-epoxy-6'-methylcyclohexanecarb Carboxylate, ε-caprolactone modified 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate, trimethylcaprolactone modified 3,4-epoxycyclohexylmethyl-3', 4'-epoxy Cyclohexanecarboxylate, β-methyl-δ-valerolactone modified 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), Di (3,4-epoxycyclohexylmethyl) ether of ethylene glycol, ethylenebis (3,4-epoxycyclohexanecarboxylate), epoxycyclohexahydrophthalic acid dioctyl and epoxycyclohexa The epoxy resin which has a di-2-ethylhexyl hydrophthalic acid and a tricyclodecene oxide group, and the compound represented by following formula (a01-1)-(a01-5) are mentioned.

In the specific example of these alicyclic epoxy compounds, the alicyclic epoxy compound represented by following formula (a01-1)-(a01-5) is preferable from giving hardened | cured material of high hardness.

[Formula 13]

(In formula (a01-1), Z ⁰¹ represents a single bond or a linking group (bivalent group having one or more atoms). R ^a01 to R ^a018 are each independently selected from the group consisting of a hydrogen atom, a halogen atom and an organic group. It is the chosen group.)

As the linking group Z ⁰¹ , for example, a divalent hydrocarbon group, -O-, -O-CO-, -S-, -SO-, -SO _2- , -CBr _2- , -C (CBr ₃ ) _2- , A divalent group selected from the group consisting of -C (CF ₃ ) _2-, and -R ^a019 -O-CO-, and a group in which a plurality of these bonds are mentioned.

As a bivalent hydrocarbon group which is the coupling group Z, a linear or branched alkylene group, a bivalent alicyclic hydrocarbon group, etc. which have C1-C18 is mentioned, for example. Examples of the linear or branched alkylene group having 1 to 18 carbon atoms include methylene group, methylene methylene group, dimethyl methylene group, dimethylene group and trimethylene group. As said bivalent alicyclic hydrocarbon group, a 1, 2- cyclopentylene group, a 1, 3- cyclopentylene group, a cyclopentylidene group, a 1, 2- cyclohexylene group, 1, 3- cyclohexylene, for example And cycloalkylene groups (including cycloalkylidene groups) such as groups, 1,4-cyclohexylene groups, and cyclohexylidene groups.

R ^a019 is an alkylene group having 1 to 8 carbon atoms, preferably a methylene group or an ethylene group.

[Formula 14]

(In formula (a01-2), R ^a01 to R ^a012 are groups selected from the group consisting of a hydrogen atom, a halogen atom and an organic group.)

[Formula 15]

(In formula (a01-3), R ^a01 to R ^a010 are a group selected from the group consisting of a hydrogen atom, a halogen atom and an organic group. R ^a02 and R ^a08 may be bonded to each other.)

[Formula 16]

(In formula (a01-4), R ^a01 to R ^a012 are groups selected from the group consisting of a hydrogen atom, a halogen atom and an organic group. R ^a02 and R ^a010 may be bonded to each other.)

[Formula 17]

(In formula (a01-5), R ^a01 to R ^a012 are a group selected from the group consisting of a hydrogen atom, a halogen atom and an organic group.)

In the formulas (a01-1) to (a01-5), when R ^a01 to R ^a018 are organic groups, the organic group is not particularly limited within the scope of not impairing the object of the present invention. The group formed may be a group containing a hetero atom such as a halogen atom, an oxygen atom, a sulfur atom, a nitrogen atom, and a silicon atom together with a carbon atom and a hydrogen atom. As an example of a halogen atom, a chlorine atom, a bromine atom, an iodine atom, a fluorine atom, etc. are mentioned.

The organic group is preferably a group consisting of a hydrocarbon group, a carbon atom, a hydrogen atom and an oxygen atom, a group consisting of a halogenated hydrocarbon group, a carbon atom, an oxygen atom and a halogen atom, and a group consisting of a carbon atom, a hydrogen atom, an oxygen atom and a halogen atom. When an organic group is a hydrocarbon group, a hydrocarbon group may be an aromatic hydrocarbon group, an aliphatic hydrocarbon group, or the group containing an aromatic skeleton and an aliphatic skeleton. 1 or more and 20 or less are preferable, as for the carbon atom number of an organic group, 1 or more and 10 or less are more preferable, and 1 or more and 5 or less are especially preferable.

Specific examples of the hydrocarbon group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, n-undecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n Chain alkyl groups such as hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group and n-icosyl group; Chain alkenyl groups such as vinyl group, 1-propenyl group, 2-n-propenyl group (allyl group), 1-n-butenyl group, 2-n-butenyl group, and 3-n-butenyl group; Cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group and cycloheptyl group; Phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, α-naphthyl group, β-naphthyl group, biphenyl-4-yl group, biphenyl-3-yl group, biphenyl-2-yl group, anthryl Aryl groups such as groups and phenanthryl groups; Aralkyl groups, such as a benzyl group, a phenethyl group, the (alpha)-naphthyl methyl group, (beta)-naphthyl methyl group, the (alpha)-naphthyl ethyl group, and (beta)-naphthyl ethyl group, are mentioned.

Specific examples of the halogenated hydrocarbon group include chloromethyl group, dichloromethyl group, trichloromethyl group, bromomethyl group, dibromomethyl group, tribromomethyl group, fluoromethyl group, difluoromethyl group, trifluoromethyl group, 2,2, 2-trifluoroethyl group, pentafluoroethyl group, heptafluoropropyl group, perfluorobutyl group and perfluoropentyl group, perfluorohexyl group, perfluoroheptyl group, perfluorooctyl group, perfluoro Halogenated chain alkyl groups such as rononyl group and perfluorodecyl group; 2-chlorocyclohexyl group, 3-chlorocyclohexyl group, 4-chlorocyclohexyl group, 2,4-dichlorocyclohexyl group, 2-bromocyclohexyl group, 3-bromocyclohexyl group and 4-bromosi Halogenated cycloalkyl groups such as a chlorhexyl group; 2-chlorophenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 2,3-dichlorophenyl group, 2,4-dichlorophenyl group, 2,5-dichlorophenyl group, 2,6-dichlorophenyl group, 3,4-dichlorophenyl group, Halogenated aryl groups such as 3,5-dichlorophenyl group, 2-bromophenyl group, 3-bromophenyl group, 4-bromophenyl group, 2-fluorophenyl group, 3-fluorophenyl group, and 4-fluorophenyl group; 2-chlorophenylmethyl group, 3-chlorophenylmethyl group, 4-chlorophenylmethyl group, 2-bromophenylmethyl group, 3-bromophenylmethyl group, 4-bromophenylmethyl group, 2-fluorophenylmethyl group, 3-fluoro Halogenated aralkyl groups such as phenylmethyl group and 4-fluorophenylmethyl group.

Specific examples of the group consisting of a carbon atom, a hydrogen atom and an oxygen atom include a hydroxy chain alkyl group such as hydroxymethyl group, 2-hydroxyethyl group, 3-hydroxy-n-propyl group and 4-hydroxy-n-butyl group. ; Halogenated cycloalkyl groups such as 2-hydroxycyclohexyl group, 3-hydroxycyclohexyl group and 4-hydroxycyclohexyl group; 2-hydroxyphenyl group, 3-hydroxyphenyl group, 4-hydroxyphenyl group, 2,3-dihydroxyphenyl group, 2,4-dihydroxyphenyl group, 2,5-dihydroxyphenyl group, 2,6-di Hydroxyaryl groups such as hydroxyphenyl group, 3,4-dihydroxyphenyl group and 3,5-dihydroxyphenyl group; Hydroxy aralkyl groups such as 2-hydroxyphenylmethyl group, 3-hydroxyphenylmethyl group and 4-hydroxyphenylmethyl group; Methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butyloxy group, isobutyloxy group, sec-butyloxy group, tert-butyloxy group, n-pentyloxy group, n-hexyl jade Period, n-heptyloxy group, n-octyloxy group, 2-ethylhexyloxy group, n-nonyloxy group, n-decyloxy group, n-undecyloxy group, n-tridecyloxy group, n-tetrade Chain alkoxy groups such as a siloxy group, n-pentadecyloxy group, n-hexadecyloxy group, n-heptadecyloxy group, n-octadecyloxy group, n-nonadecyloxy group and n-icosyloxy group; Vinyloxy group, 1-propenyloxy group, 2-n-propenyloxy group (allyloxy group), 1-n-butenyloxy group, 2-n-butenyloxy group and 3-n-butenyloxy group Chain alkenyloxy group; Phenoxy group, o-tolyloxy group, m-tolyloxy group, p-tolyloxy group, α-naphthyloxy group, β-naphthyloxy group, biphenyl-4-yloxy group, biphenyl-3-yloxy group, non Aryloxy groups such as phenyl-2-yloxy group, anthryloxy group and phenanthryloxy group; Aralkyloxy groups such as benzyloxy group, phenethyloxy group, α-naphthylmethyloxy group, β-naphthylmethyloxy group, α-naphthylethyloxy group and β-naphthylethyloxy group; Methoxymethyl group, ethoxymethyl group, n-propoxymethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 2-n-propoxyethyl group, 3-methoxy-n-propyl group, 3-ethoxy-n Alkoxy such as -propyl group, 3-n-propoxy-n-propyl group, 4-methoxy-n-butyl group, 4-ethoxy-n-butyl group and 4-n-propoxy-n-butyl group Alkyl groups; Methoxymethoxy group, ethoxymethoxy group, n-propoxymethoxy group, 2-methoxyethoxy group, 2-ethoxyethoxy group, 2-n-propoxyethoxy group, 3-methoxy-n- Propoxy group, 3-ethoxy-n-propoxy group, 3-n-propoxy-n-propoxy group, 4-methoxy-n-butyloxy group, 4-ethoxy-n-butyloxy group and Alkoxyalkoxy groups such as 4-n-propoxy-n-butyloxy group; Alkoxyaryl groups such as 2-methoxyphenyl group, 3-methoxyphenyl group and 4-methoxyphenyl group; Alkoxyaryloxy groups such as 2-methoxyphenoxy group, 3-methoxyphenoxy group and 4-methoxyphenoxy group; Aliphatic acyl groups such as formyl group, acetyl group, propionyl group, butanoyl group, pentanoyl group, hexanoyl group, heptanoyl group, octanoyl group, nonanoyl group and decanoyl group; Aromatic acyl groups such as benzoyl group, α-naphthoyl group and β-naphthoyl group; Methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, n-butyloxycarbonyl group, n-pentyloxycarbonyl group, n-hexylcarbonyl group, n-heptyloxycarbonyl group, n-octyloxycarbonyl group, n-nonyloxycarbonyl group and n Linear alkyloxycarbonyl groups such as decyloxycarbonyl group; Aryloxycarbonyl groups such as phenoxycarbonyl group, α-naphthoxycarbonyl group and β-naphthoxycarbonyl group; Aliphatic acyloxy groups such as formyloxy group, acetyloxy group, propionyloxy group, butanoyloxy group, pentanoyloxy group, hexanoyloxy group, heptanoyloxy group, octanoyloxy group, nonanoyloxy group and decanoyloxy group; Aromatic acyloxy groups such as benzoyloxy group, α-naphthoyloxy group and β-naphthoyloxy group.

R ^a01 to R ^a018 are each independently a group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, and an alkoxy group having 1 to 5 carbon atoms, and particularly have a mechanical property. Since it is easy to form the excellent cured film, it is more preferable that all of R ^a01 -R ^a018 are hydrogen atoms.

In formulas (a01-2) to (a01-5), R ^a01 to R ^a012 are the same as R ^a01 to R ^a012 in formula (a01-1). In the formulas (a01-2) and (a01-4), examples of the divalent group formed when R ^a02 and R ^a010 combine with each other include, for example, -CH ₂ -and -C (CH ₃ ) _2. -Can be mentioned. In formula (a01-3), examples of the divalent group formed when R ^a02 and R ^a08 are bonded to each other include -CH ₂ -and -C (CH ₃ ) _2- .

Among the alicyclic epoxy compounds represented by formula (a01-1), specific examples of suitable compounds include alicyclic epoxy represented by the following formulas (a01-1a), (a01-1b) and (a01-1c). A compound, 2, 2-bis (3, 4- epoxy cyclo hexane- 1-yl) propane [= 2, 2-bis (3, 4- epoxy cyclohexyl) propane], etc. are mentioned.

[Formula 18]

Among the alicyclic epoxy compounds represented by the formula (a01-2), examples of suitable compounds include bicyclononadiene diepoxide or dicyclononadiene diepoxide represented by the following formula (a01-2a). have.

[Formula 19]

Among the alicyclic epoxy compounds represented by the formula (a01-3), specific examples of suitable compounds include Sspiro [3-oxatricyclo [3.2.1.0 ^2,4 ] octane-6,2'-oxirane] and the like. Can be mentioned.

In the alicyclic epoxy compound represented by formula (a01-4), as a specific example of a suitable compound, 4-vinyl cyclohexene dioxide, dipentene dioxide, limonene dioxide, 1-methyl-4- (3-methyl) Oxirane-2-yl) -7-oxabicyclo [4.1.0] heptane and the like.

In the alicyclic epoxy compound represented by formula (a01-5), 1,2,5,6-diepoxycyclooctane etc. are mentioned as a specific example of a preferable compound.

Precursor Resin

As a base material component (A), the precursor resin which is resin which produces the aromatic ring formation reaction in a molecule | numerator, and / or the crosslinking reaction between molecules by heating is preferable.

According to the aromatic ring formation reaction in the molecule, the structure of the molecular chain constituting the resin can be rigid, and a hydrogen barrier film excellent in heat resistance and mechanical properties can be formed. As a preferable reaction among the aromatic ring formation reaction in a molecule | numerator, reaction represented by following formula (I)-(VI) is mentioned, for example. In addition, the reaction in the following formula is only an example of an aromatic ring formation reaction, and the structure of resin which produces the aromatic ring formation reaction in a molecule | numerator by heating used as a base material component (A) is represented by the following formula. It is not limited to the structure of a polymer.

[Formula 20]

(Resin which has group chosen from hydroxyl group, carboxylic anhydride group, carboxyl group and epoxy group in molecule)

According to the crosslinking reaction between molecules, the molecular chains constituting the resin are crosslinked with each other to form a three-dimensional crosslinked structure. For this reason, when the resin which has a group chosen from a hydroxyl group, a carboxylic anhydride group, a carboxyl group, and an epoxy group in a molecule | numerator which produces a crosslinking reaction by heating is used as a base component (A), the hydrogen barrier film excellent in heat resistance and a mechanical characteristic is obtained. .

In the case of using a resin having a hydroxyl group, crosslinking due to dehydration condensation between hydroxyl groups occurs between molecules contained in the resin due to the action of the dehydrating condensing agent. Moreover, since a hydroxyl group contains active hydrogen atom and is rich in reactivity, it reacts with various crosslinking agents, and provides the hardened | cured material containing crosslinked resin.

In the case of using a resin having a carboxylic anhydride group, carboxyl groups formed by hydrolysis of an acid anhydride group are dehydrated and crosslinked by the action of a dehydrating condensing agent. Moreover, since acid anhydride group itself is also rich in reactivity, the hardened | cured material containing crosslinked resin is provided by using crosslinking agents, such as the polyol which has two or more hydroxyl groups, and the polyamine which has two or more amino groups, for example.

In the case of using a resin having a carboxyl group, crosslinking occurs due to dehydration and condensation between carboxyl groups between molecules contained in the resin due to the action of the dehydrating condensing agent. Moreover, it can also be bridge | crosslinked using the crosslinking agent which has a functional group which can react with a carboxyl group like an isocyanate group.

When using resin which has an epoxy group, if necessary, by using a well-known hardening accelerator etc., bridge | crosslinking by the polyaddition reaction between epoxy groups arises between the molecules contained in resin.

As resin which has a hydroxyl group in a molecule | numerator, a novolak resin is mentioned, for example. Although it does not specifically limit as a novolak resin, Resin obtained by making condensation reaction of condensing agents, such as formaldehyde and a paraformaldehyde, at 0.5 mol or more and 1.0 mol or less with respect to 1 mol of phenols under an acidic catalyst is preferable.

As phenols, For example, cresols, such as a phenol, o-cresol, m-cresol, p-cresol; X, such as 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol Silenols; ethylphenols such as o-ethylphenol, m-ethylphenol and p-ethylphenol, 2-isopropylphenol, 3-isopropylphenol, 4-isopropylphenol, o-butylphenol, m-butylphenol, p-butyl Alkyl phenols such as phenol and p-tert-butylphenol; Trialkylphenols such as 2,3,5-trimethylphenol and 3,4,5-trimethylphenol; Polyhydric phenols such as resorcinol, catechol, hydroquinone, hydroquinone monomethyl ether, pyrogarol and fluoroglycinol; Alkyl polyhydric phenols, such as alkylesolcin, alkyl catechol, and alkyl hydroquinone (The number of carbon atoms of the alkyl group contained in alkyl polyhydric phenols is 1 or more and 4 or less.), (Alpha) -naphthol, (beta) -naphthol, hydroxydiphenyl, bisphenol A etc. can be mentioned. These phenols can be used individually or in combination of 2 or more types.

Among phenols, m-cresol and p-cresol are preferable, and it is more preferable to use m-cresol and p-cresol together. By adjusting the compounding ratio of both, various characteristics such as sensitivity as the photoresist and heat resistance can be adjusted. Although the compounding ratio of m-cresol and p-cresol is not specifically limited, m-cresol / p-cresol = 3/7 or more and 8/2 or less (mass ratio) are preferable. When the ratio of m-cresol becomes less than the said lower limit, sensitivity may fall, and when it exceeds the said upper limit, heat resistance may fall.

As an acidic catalyst used for manufacture of a novolak resin, For example, inorganic acids, such as hydrochloric acid, a sulfuric acid, nitric acid, phosphoric acid, a phosphoric acid, organic acids, such as formic acid, an oxalic acid, acetic acid, diethylsulfonic acid, a paratoluenesulfonic acid, and acetic acid Metal salts such as zinc; and the like. These acidic catalysts can be used individually or in combination of 2 or more types.

As for the mass mean molecular weight of the novolak resin by polystyrene conversion by a gel permeation chromatography (GPC) measurement, 1,000 or more and 50,000 or less are preferable.

As resin which has a carboxylic anhydride group in a molecule | numerator, the copolymer obtained by superposing | polymerizing the mixture of the monomer which has an unsaturated double bond containing 1 or more types of monomers chosen from maleic anhydride, citraconic anhydride, and itaconic anhydride is preferable. As such a polymer, a styrene-maleic acid copolymer is preferable.

As a resin which has a carboxyl group in a molecule | numerator, resin obtained by hydrolyzing the acid anhydride group in resin which has a carboxylic anhydride group in the molecule mentioned above, (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, and ita Preferred is a copolymer obtained by polymerizing a mixture of monomers having an unsaturated double bond, comprising at least one monomer selected from cholic acid.

The epoxy group-containing resin having an epoxy group in the molecule will be described later in detail.

Among such compounds which cause an aromatic ring formation reaction in a molecule or a crosslinking reaction between molecules due to such heating, a polyamic acid, a polybenzoxazole precursor, and a polybenzoate are easily formed from a hydrogen barrier film having excellent heat resistance. Thiazole precursors, polybenzoimidazole precursors, styrene-maleic acid copolymers and epoxy group-containing resins are preferred. Hereinafter, these resins are demonstrated.

[Styrene-maleic acid copolymer]

The kind of styrene-maleic acid copolymer is not specifically limited in the range which does not impair the objective of this invention. The copolymerization ratio (mass ratio) of styrene / maleic acid in the styrene-maleic acid copolymer is preferably 1/9 or more and 9/1 or less, more preferably 2/8 or more and 8/1 or less, more preferably 1/1 or more 8/1 or less is especially preferable. Although the molecular weight of a styrene-maleic acid copolymer is not specifically limited, It is preferable that it is 1,000 or more and 100,000 or less as a mass average molecular weight in polystyrene conversion, and it is more preferable that it is 5,000 or more and 12,000 or less.

[Epoxy group-containing resin]

When epoxy group containing resin is used as a base material component (A), the epoxy groups which epoxy group containing resin has bridge | crosslink by heating in presence of a hardening | curing agent and a hardening accelerator as needed. As a result, a cured product excellent in heat resistance and mechanical properties is obtained. An epoxy group containing resin will not be specifically limited if it is resin comprised from the molecule which has an epoxy group.

The epoxy group-containing resin may be a polymer obtained by polymerizing a monomer mixture containing a monomer having an epoxy group or a monomer having an epoxy group. Epoxy-group containing resin may introduce | transduce an epoxy group using the compound which has an epoxy group, such as epichlorohydrin, with respect to the polymer which has functional groups, such as a hydroxyl group, a carboxy group, and an amino group, for example. As a polymer which has an epoxy group, the polymer obtained by superposing | polymerizing the monomer mixture containing the monomer which has an epoxy group, or the monomer which has an epoxy group is preferable from acquisition, preparation, adjustment of the quantity of the epoxy group in a polymer, etc. is easy.

As a preferable example of an epoxy-group-containing resin, furnaces, such as a phenol novolak-type epoxy resin, a brominated phenol novolak-type epoxy resin, an ortho cresol novolak-type epoxy resin, a bisphenol A novolak-type epoxy resin, and a bisphenol AD novolak-type epoxy resin Volac epoxy resins; Cyclic aliphatic epoxy resins such as epoxides of dicyclopentadiene type phenol resins; Aromatic epoxy resins, such as the epoxide of a naphthalene type phenol resin, are mentioned.

Moreover, in epoxy-group-containing resin, since preparation is easy or adjustment of the physical property of a hydrogen barrier film is easy, it is a homopolymer of (meth) acrylic acid ester which has an epoxy group, or with monomers other than (meth) acrylic acid ester which has an epoxy group. Copolymers are preferred.

The (meth) acrylic acid ester which has an epoxy group may be (meth) acrylic acid ester which has a chain aliphatic epoxy group, or the (meth) acrylic acid ester which has an alicyclic epoxy group mentioned later may be sufficient as it. Moreover, the (meth) acrylic acid ester which has an epoxy group may contain the aromatic group. In the (meth) acrylic acid ester which has an epoxy group, the aliphatic (meth) acrylic acid ester which has a chain aliphatic epoxy group, and the aliphatic (meth) acrylic acid ester which has an alicyclic epoxy group are preferable, and the aliphatic (meth) acrylic acid ester which has an alicyclic epoxy group More preferably, from the viewpoint of the patterning characteristics, the aliphatic (meth) acrylic acid ester having an alicyclic epoxy group having a polycyclic structure in the ring structure in the alicyclic epoxy group is more preferable.

Examples of the (meth) acrylic acid ester containing an aromatic group and having an epoxy group include 4-glycidyloxyphenyl (meth) acrylate, 3-glycidyloxyphenyl (meth) acrylate, and 2-glycidyloxyphenyl (Meth) acrylate, 4-glycidyloxyphenylmethyl (meth) acrylate, 3-glycidyloxyphenylmethyl (meth) acrylate, 2-glycidyloxyphenylmethyl (meth) acrylate, and the like. Can be.

Examples of aliphatic (meth) acrylic acid esters having a chain aliphatic epoxy group include oxy group (-O) in an ester group (-O-CO-) such as epoxyalkyl (meth) acrylate and epoxyalkyloxyalkyl (meth) acrylate. (Meth) acrylic acid ester which a chain | strand aliphatic epoxy group couple | bonds with-) is mentioned. The chain aliphatic epoxy group which such (meth) acrylic acid ester has may contain 1 or several oxy group (-O-) in a chain. Although the number of carbon atoms of a linear aliphatic epoxy group is not specifically limited, 3 or more and 20 or less are preferable, 3 or more and 15 or less are more preferable, 3 or more and 10 or less are especially preferable.

As a specific example of the aliphatic (meth) acrylic acid ester which has a chain aliphatic epoxy group, glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 3, 4- epoxy butyl (meth) acrylate, Epoxyalkyl (meth) acrylates such as 6,7-epoxyheptyl (meth) acrylate; 2-glycidyloxyethyl (meth) acrylate, 3-glycidyloxy-n-propyl (meth) acrylate, 4-glycidyloxy-n-butyl (meth) acrylate, 5-glycidyl Epoxy alkyloxy alkyl (meth) acrylates, such as oxy-n-hexyl (meth) acrylate and 6-glycidyloxy-n-hexyl (meth) acrylate, are mentioned.

As a specific example of aliphatic (meth) acrylic acid ester which has an alicyclic epoxy group, the compound represented, for example by following formula (a05-1)-(a05-15) is mentioned. Among these, the compounds represented by the following formulas (a05-1) to (a05-5) are preferable, and the compounds represented by the following formulas (a05-1) to (a05-2) are more preferable. Moreover, about each of these compounds, the bonding site | part of the oxygen atom of the ester group with respect to an alicyclic is not limited to the position shown here, and may contain some positional isomer.

[Formula 21]

[Formula 22]

[Formula 23]

In the above formula, R ^a032 represents a hydrogen atom or a methyl group, R ^a033 represents a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, R ^a034 represents a divalent hydrocarbon group having 1 to 10 carbon atoms, t ⁰ represents an integer of 0 or more and 10 or less. As R <^a033> , a linear or branched alkylene group, for example, methylene group, ethylene group, propylene group, tetramethylene group, ethylethylene group, pentamethylene group, and hexamethylene group is preferable. As R ^a034 , a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group, a hexamethylene group, a phenylene group, and a cyclohexylene group are preferable, for example.

As a polymer which has an epoxy group, either the homopolymer of the (meth) acrylic acid ester which has an epoxy group, and the copolymer of the (meth) acrylic acid ester which has an epoxy group, and another monomer can be used, but the epoxy group in the polymer which has an epoxy group Content of the unit derived from the (meth) acrylic acid ester which has is 1-100 mass%, for example, 10 mass% or more and 90 mass% or less are preferable, 30 mass% or more and 80 mass% or less are more preferable, 50 Particularly preferred is mass% or more and 75 mass% or less.

When the polymer which has an epoxy group is a copolymer of the (meth) acrylic acid ester which has an epoxy group, and another monomer, As another monomer, Unsaturated carboxylic acid, (meth) acrylic acid ester which does not have an epoxy group, (meth) acrylamide, allyl compound, vinyl Ethers, vinyl esters, styrene, etc. are mentioned. These compounds can be used individually or in combination of 2 or more types. In view of chemical stability against storage stability of the composition for forming a hydrogen barrier film and alkali of a hydrogen barrier film formed using the composition for forming a hydrogen barrier film, a copolymer of a (meth) acrylic acid ester having an epoxy group with another monomer is It is preferable not to include the unit derived from unsaturated carboxylic acid.

Examples of the unsaturated carboxylic acid include (meth) acrylic acid; (Meth) acrylic acid amide; Crotonic acid; Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, and anhydrides of these dicarboxylic acids.

As an example of the (meth) acrylic acid ester which does not have an epoxy group, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, amyl (meth) acrylate, t-octyl (meth) acrylate, etc. Linear or branched alkyl (meth) acrylates of; Chloroethyl (meth) acrylate, 2,2-dimethylhydroxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, trimethylolpropane mono (meth) acrylate, benzyl (meth) acrylate, Perfuryl (meth) acrylate; (Meth) acrylic acid ester which has group which has alicyclic skeleton is mentioned. In the (meth) acrylic acid ester which does not have an epoxy group, the (meth) acrylic acid ester which has group which has an alicyclic skeleton is preferable.

In the (meth) acrylic acid ester having a group having an alicyclic skeleton, the alicyclic group constituting the alicyclic skeleton may be monocyclic or polycyclic. Cyclopentyl group, cyclohexyl group, etc. are mentioned as monocyclic alicyclic group. Moreover, as a polycyclic alicyclic group, a norbornyl group, an isobornyl group, a tricyclononyl group, a tricyclodecyl group, a tetracyclo dodecyl group, etc. are mentioned.

As (meth) acrylic acid ester which has group which has alicyclic skeleton, the compound represented, for example by following formula (a06-1)-(a06-8) is mentioned. In these, the compound represented by following formula (a06-3)-(a06-8) is preferable, and the compound represented by following formula (a06-3) or (a06-4) is more preferable.

[Formula 24]

[Formula 25]

In the above formula, R ^a035 represents a hydrogen atom or a methyl group, R ^a036 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, and R ^a037 represents a hydrogen atom or 1 to 5 carbon atoms. An alkyl group is shown. As R ^a036 , a single bond, linear or branched alkylene group, for example, methylene group, ethylene group, propylene group, tetramethylene group, ethylethylene group, pentamethylene group, and hexamethylene group is preferable. As R ^a037 , a methyl group and an ethyl group are preferable.

Examples of (meth) acrylamides include (meth) acrylamide, N-alkyl (meth) acrylamide, N-aryl (meth) acrylamide, N, N-dialkyl (meth) acrylamide, N, N- Aryl (meth) acrylamide, N-methyl-N-phenyl (meth) acrylamide, N-hydroxyethyl-N-methyl (meth) acrylamide, etc. are mentioned.

Examples of the allyl compound include allyl esters such as allyl acetate, allyl caproic acid, allyl caprylic acid, allyl laurate, allyl palmitate, allyl stearic acid, allyl benzoate, allyl acetoacetate, and allyl lactate; Allyloxyethanol; Etc. can be mentioned.

Examples of vinyl ethers include hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethyl hexyl vinyl ether, methoxy ethyl vinyl ether, ethoxy ethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethyl Propyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl Aliphatic vinyl ethers such as vinyl ether; Vinyl aryl ethers such as vinyl phenyl ether, vinyl tolyl ether, vinyl chloro phenyl ether, vinyl-2,4-dichlorophenyl ether, vinyl naphthyl ether and vinyl enthranyl ether; Etc. can be mentioned.

Examples of vinyl esters include vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valerate, vinyl caproate, vinyl chloro acetate, vinyl dichloro acetate, vinyl methoxy acetate, vinyl butoxy acetate, vinyl Phenyl acetate, vinyl acetoacetate, vinyl lactate, vinyl-β-phenylbutyrate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthoate, and the like.

Examples of styrenes include styrene; Methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, isopropyl styrene, butyl styrene, hexyl styrene, cyclohexyl styrene, decyl styrene, benzyl styrene, chloromethyl styrene, trifluoromethyl styrene, ethoxymethyl styrene Alkyl styrene such as acetoxymethyl styrene; Alkoxy styrenes such as methoxy styrene, 4-methoxy-3-methyl styrene and dimethoxy styrene; Chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoro Halostyrenes such as methyl styrene and 4-fluoro-3-trifluoromethyl styrene; Etc. can be mentioned.

Although the molecular weight of epoxy group containing resin is not specifically limited in the range which does not impair the objective of this invention, As a mass mean molecular weight of polystyrene conversion, 3,000 or more and 30,000 or less are preferable, and 5,000 or more and 15,000 or less are more preferable.

When using the said thermosetting material as a base material component (A), the composition for hydrogen barrier film formation is a hardening | curing agent, a hardening accelerator, a dehydration condensing agent, antioxidant, a ultraviolet absorber, a flame retardant, a mold release agent, a plasticizer, a filler, and a reinforcement material as needed. You may contain additives and reinforcing materials, such as these.

Moreover, in order to make film forming easy, the composition for hydrogen barrier film formation may contain the solvent. The kind of solvent is suitably selected according to the kind of thermosetting material.

When the composition for forming a hydrogen barrier film contains the thermosetting material and the hydrogen barrier agent (B), the content of the hydrogen barrier agent is 0.01% by mass or more and 30% by mass with respect to the mass of the thermosetting material of the composition for forming a hydrogen barrier film. % Or less is preferable, 0.05 mass% or more and 20 mass% or less are more preferable, 0.1 mass% or more and 10 mass% or less are especially preferable.

As a composition for forming a hydrogen barrier film, in addition to the composition containing the base component (A) described above, a photosensitive composition known as a so-called photoresist composition is also preferable. By adding a predetermined amount of the above-described hydrogen barrier agent (B) to various conventionally known photosensitive compositions, a composition for forming a photosensitive hydrogen barrier film is obtained.

Conventionally known photosensitive compositions include various photocurable compounds, alkali-soluble resins, resins which increase the solubility in alkali by exposure, and the like as the base component (A).

The photosensitive hydrogen barrier film-forming composition may be a negative photosensitive composition that is insolubilized with a developer by exposure, or a positive photosensitive composition that is solubilized with a developer by exposure.

Hereinafter, a suitable photosensitive composition is demonstrated.

(1) The photosensitive composition of a 1st aspect

The photosensitive composition of a 1st aspect is a negative photosensitive composition containing a hydrogen barrier agent (B) and an organic solvent with alkali-soluble resin (A1), a photopolymerizable compound (A2), and a photoinitiator (C).

In the photosensitive composition of a 1st aspect, alkali-soluble resin (A1) and a photopolymerizable compound (A2) correspond to a base material component (A).

It does not specifically limit as alkali-soluble resin (A1) in the photosensitive composition of a 1st aspect, Conventionally well-known alkali-soluble resin can be used. This alkali-soluble resin (A1) may have an ethylenically unsaturated group, and does not need to have an ethylenically unsaturated group.

In addition, in this specification, an alkali-soluble resin is formed with the resin solution (solvent: propylene glycol monomethyl ether acetate) of 20 mass% of resin concentration, and forms the resin film of 1 micrometer in thickness on a board | substrate, and it is 2.38 mass% tetra When immersed in aqueous methylammonium hydroxide (TMAH) solution for 1 minute, it refers to resin which melt | dissolves 0.01 micrometer or more in film thickness.

As alkali-soluble resin (A1) which has an ethylenically unsaturated group, resin obtained by making the reactant of an epoxy compound and unsaturated carboxylic acid further react with polybasic acid anhydride can be used, for example.

Especially, resin represented by following formula (a-1) is preferable. Resin represented by this formula (a-1) is preferable at the point which itself has high photocurability.

[Formula 26]

In the formula ^(a-1), X a represents a group represented by the following formula (a-2).

[Formula 27]

In said formula (a-2), R <^a1> represents a hydrogen atom, a C1-C6 hydrocarbon group, or a halogen atom each independently, R <^a2> represents a hydrogen atom or a methyl group each independently, W ^<a> The group represented by a single bond or following formula (a-3) is shown.

[Formula 28]

In addition, it represents the formula (a-1) of, Y is ^a moiety other than an acid anhydride group (-CO-O-CO-) from the dicarboxylic acid anhydride. Examples of the dicarboxylic acid anhydride include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylendmethylenetetrahydrophthalic anhydride, chloric anhydride, methyltetrahydrophthalic anhydride, Glutaric anhydride etc. are mentioned.

Further, In the formula ^(a-1), Z a represents a moiety other than an acid anhydride in a two tetracarboxylic acid dianhydride. Examples of tetracarboxylic dianhydride include pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, biphenyl ether tetracarboxylic dianhydride and the like.

In addition, in said formula (a-1), m shows the integer of 0-20.

Moreover, as alkali-soluble resin (A1) which has an ethylenically unsaturated group, Polyester (meth) acrylate obtained by making (meth) acrylic acid react with the polyester prepolymer obtained by condensing polyhydric alcohol and monobasic acid or polybasic acid; Polyurethane (meth) acrylates obtained by reacting a polyol with a compound having two isocyanate groups and then reacting (meth) acrylic acid; Bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol or cresol novolak type epoxy resin, resol type epoxy resin, triphenol methane type epoxy resin, polycarboxylic acid polyglycidyl ester, polyol polyglycol Epoxy (meth) acrylate resin etc. which are obtained by making (meth) acrylic acid react with epoxy resins, such as a cydyl ester, an aliphatic or alicyclic epoxy resin, an amine epoxy resin, and a dihydroxy benzene type epoxy resin, can also be used.

In addition, in this specification, "(meth) acrylic acid" means both acrylic acid and methacrylic acid. Similarly, "(meth) acrylate" means both an acrylate and a methacrylate.

On the other hand, as alkali-soluble resin (A1) which does not have an ethylenically unsaturated group, resin obtained by copolymerizing unsaturated carboxylic acid and another unsaturated compound can be used. As another unsaturated compound, it is preferable to use at least 1 sort (s) chosen from an epoxy group containing unsaturated compound and an alicyclic group containing unsaturated compound.

As unsaturated carboxylic acid, Monocarboxylic acids, such as (meth) acrylic acid and crotonic acid; Dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid; Anhydrides of these dicarboxylic acids; Etc. can be mentioned. Among these, (meth) acrylic acid and maleic anhydride are preferable from the viewpoints of copolymerization reactivity, alkali solubility of resin obtained, availability, and the like. These unsaturated carboxylic acids can be used individually or in combination of 2 or more types.

As an epoxy group containing unsaturated compound, the epoxy group containing unsaturated compound which does not have an alicyclic group, and the epoxy group containing unsaturated compound which has an alicyclic group are mentioned.

As an epoxy-group containing unsaturated compound which has an alicyclic group, the compound represented by above-mentioned Formula (a05-1)-(a05-15) is mentioned.

As an epoxy group containing unsaturated compound which does not have an alicyclic group, glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 3, 4- epoxy butyl (meth) acrylate, 6,7-epoxy Epoxy alkyl (meth) acrylates such as heptyl (meth) acrylate; 2-glycidyloxyethyl (meth) acrylate, 3-glycidyloxy-n-propyl (meth) acrylate, 4-glycidyloxy-n-butyl (meth) acrylate, 5-glycidyl Epoxyalkyloxyalkyl (meth) acrylates such as oxy-n-pentyl (meth) acrylate and 6-glycidyloxy-n-hexyl (meth) acrylate; α-alkyl acrylate epoxyalkyl esters such as α-ethyl acrylate glycidyl, α-n-propyl acrylate glycidyl, α-n-butyl acrylate glycidyl and α-ethyl acrylate 6,7-epoxyheptyl; glycidyl ethers such as o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether and p-vinyl benzyl glycidyl ether; Etc. can be mentioned. Among these, glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 6,7-epoxyheptyl (meth) acrylate, o from the point of copolymerization reactivity, the strength of resin after hardening, etc., o -Vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether and p-vinyl benzyl glycidyl ether are preferable.

These epoxy group containing unsaturated compounds can be used individually or in combination of 2 or more types.

It will not specifically limit, if it is an unsaturated compound which has an alicyclic group as an alicyclic group containing unsaturated compound. The alicyclic group may be monocyclic or polycyclic. Cyclopentyl group, cyclohexyl group, etc. are mentioned as monocyclic alicyclic group. Moreover, as a polycyclic alicyclic group, an adamantyl group, norbornyl group, isobornyl group, tricyclononyl group, tricyclodecyl group, tetracyclododecyl group, etc. are mentioned. Specifically, as an alicyclic group containing unsaturated compound, the compound represented, for example by Formula (a06-1) (a06-8) mentioned above is mentioned.

It is also preferable to further superpose | polymerize another compound of that excepting the above about unsaturated carboxylic acid. Examples of such other compounds include (meth) acrylic acid esters, (meth) acrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes, maleimides, and the like. These compounds can be used individually or in combination of 2 or more types.

As (meth) acrylic acid ester, linear (such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, amyl (meth) acrylate, t-octyl (meth) acrylate), or Branched alkyl (meth) acrylates; Chloroethyl (meth) acrylate, 2,2-dimethylhydroxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, trimethylolpropane mono (meth) acrylate, benzyl (meth) acrylate, Perfuryl (meth) acrylate; Etc. can be mentioned.

As (meth) acrylamide, (meth) acrylamide, N-alkyl (meth) acrylamide, N-aryl (meth) acrylamide, N, N-dialkyl (meth) acrylamide, N, N-aryl (Meth) acrylamide, N-methyl-N-phenyl (meth) acrylamide, N-hydroxyethyl-N-methyl (meth) acrylamide, etc. are mentioned.

Examples of the allyl compound include allyl esters such as allyl acetate, allyl caproic acid, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, and allyl lactate; Allyloxyethanol; Etc. can be mentioned.

As vinyl ether, hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxy ethyl vinyl ether, ethoxy ethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl Vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl Alkyl vinyl ethers such as ether; Vinyl aryl ethers such as vinyl phenyl ether, vinyl tolyl ether, vinyl chloro phenyl ether, vinyl-2,4-dichlorophenyl ether, vinyl naphthyl ether and vinyl enthranyl ether; Etc. can be mentioned.

As vinyl esters, vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valerate, vinyl caproate, vinyl chloro acetate, vinyl dichloro acetate, vinyl methoxy acetate, vinyl butoxy acetate, vinyl phenyl Acetates, vinyl acetoacetate, vinyl lactate, vinyl-β-phenylbutyrate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthoate, and the like.

As styrene, Styrene; Methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, isopropyl styrene, butyl styrene, hexyl styrene, cyclohexyl styrene, decyl styrene, benzyl styrene, chloromethyl styrene, trifluoromethyl styrene, ethoxymethyl styrene Alkyl styrene such as acetoxymethyl styrene; Alkoxy styrenes such as methoxy styrene, 4-methoxy-3-methyl styrene and dimethoxy styrene; Chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoro Halostyrenes such as methyl styrene and 4-fluoro-3-trifluoromethyl styrene; Etc. can be mentioned.

As maleimide, N-methyl maleimide, N-ethyl maleimide, Nn-propyl maleimide, N-isopropyl maleimide, Nn-butyl maleimide, Nn-pentyl maleimide, Nn-hexyl maleimide, etc. Maleimide N-substituted by an alkyl group having 1 to 10 carbon atoms; Maleimide N-substituted by C3 or more and 20 or less alicyclic groups, such as N-cyclopentyl maleimide, N-cyclohexyl maleimide, and N-cycloheptyl maleimide: N-phenyl maleimide, N-alpha-naph N-arylmaleimide N-substituted by an aryl group having 6 to 20 carbon atoms, such as tilmaleimide and N-β-naphthylmaleimide; N-aralkyl maleimide N-substituted by the aralkyl group of seven or more carbon atoms, such as N-benzyl maleimide and N-phenethylmaleimide, is mentioned.

Moreover, it originates in the copolymer which has at least the structural unit which has a polymerizable site | part with a photopolymerizable compound (A2) mentioned later with the structural unit derived from unsaturated carboxylic acid, or the structural unit derived from unsaturated carboxylic acid, and an epoxy group containing unsaturated compound. The copolymer which has at least a structural unit which has a polymerizable site | part of the structural unit mentioned and a photopolymerizable compound (A2) mentioned later can also be used suitably as alkali-soluble resin (A1).

When using these alkali-soluble resin, the hydrogen barrier film | membrane which is excellent in mechanical strength and excellent in adhesiveness with respect to a board | substrate can be formed.

The copolymer which has a structural unit which has a polymerizable site | part with said photopolymerizable compound (A2) is (meth) acrylic acid ester, (meth) acrylamide, allyl compound, vinyl ether, vinyl ester, You may further have 1 or more types of structural units derived from styrene, maleimide, etc.

It is preferable that the structural unit which has a polymerizable site | part with a photopolymerizable compound (A2) has an ethylenically unsaturated group as a polymerizable site | part with a photopolymerizable compound (A2). The copolymer which has such a structural unit can be prepared by making at least one part of the carboxyl groups contained in the homopolymer of unsaturated carboxylic acid, and an epoxy group containing unsaturated compound react.

Moreover, even if it reacts at least one part of the epoxy group and unsaturated carboxylic acid in the copolymer which has a structural unit derived from unsaturated carboxylic acid, and a structural unit derived from an epoxy group containing unsaturated compound, it has a site | part which can superpose | polymerize with a photopolymerizable compound (A2). The copolymer which has a structural unit can be prepared.

It is preferable that it is 3 mass% or more and 25 mass% or less, and, as for the ratio of the structural unit derived from the said unsaturated carboxylic acid in this alkali-soluble resin (A1), it is more preferable that it is 5 mass% or more and 25 mass% or less. Moreover, it is preferable that it is 30 mass% or more and 95 mass% or less, and, as for the ratio of the structural unit derived from the said epoxy group containing unsaturated compound, it is more preferable that it is 50 mass% or more and 90 mass% or less. Moreover, it is preferable that the ratio of the structural unit derived from the said alicyclic group containing unsaturated compound is 1 mass% or more and 30 mass% or less, It is more preferable that they are 3 mass% or more and 25 mass% or less, It is 5 mass% or more and 20 mass% or less More preferred. By setting it as said range, adhesiveness with respect to the board | substrate of the photosensitive composition and the intensity | strength after hardening of the photosensitive composition can be made high, making alkali solubility of resin obtained appropriate.

It is preferable that it is 1,000 or more and 40,000 or less, and, as for the mass mean molecular weight of alkali-soluble resin (A1), it is more preferable that it is 2,000 or more and 30,000 or less. By setting it as said range, sufficient heat resistance and film strength can be obtained, obtaining favorable developability.

It is preferable that it is 5 mass% or more and 80 mass% or less with respect to solid content of the photosensitive composition of a 1st aspect, and, as for content of alkali-soluble resin (A1), it is more preferable that it is 15 mass% or more and 50 mass% or less. By setting it as said range, there exists a tendency which is easy to obtain the balance of developability.

As a photopolymerizable compound (A2) in the photosensitive composition of a 1st aspect, there exist a monofunctional monomer and a polyfunctional monomer.

As a monofunctional monomer, (meth) acrylamide, methylol (meth) acrylamide, methoxymethyl (meth) acrylamide, ethoxymethyl (meth) acrylamide, propoxymethyl (meth) acrylamide, butoxymeth Methoxymethyl (meth) acrylamide, N-methylol (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, (meth) acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, Citraconic acid, citraconic anhydride, crotonic acid, 2-acrylamide-2-methylpropanesulfonic acid, tert-butylacrylamide sulfonic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate , 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylic 2-phenoxy-2-hydroxypropyl (meth) acrylic , 2- (meth) acryloyloxy-2-hydroxypropyl phthalate, glycerin mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dimethylaminoethyl (meth) acrylate, glycidyl (meth ) Acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, half (meth) acrylate of a phthalic acid derivative, etc. are mentioned. Can be. These monofunctional monomers can be used individually or in combination of 2 or more types.

On the other hand, as a polyfunctional monomer, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (Meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexane glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerin Di (meth) acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol di (meth) acrylate, pentaerythritol Tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol Hexa (meth) acrylate, 2,2-bis (4- (meth) acryloxydiethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxypolyethoxyphenyl) propane, 2-hydroxy -3- (meth) acryloyloxypropyl (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, diglycidyl phthalate Dyl ester di (meth) acrylate, glycerin triacrylate, glycerin polyglycidyl ether poly (meth) acrylate, urethane (meth) acrylate (ie, tolylene diisocyanate), trimethylhexamethylene diisocyanate and hexamethylene di Polyfunctionality, such as the reaction product of isocyanate and 2-hydroxyethyl (meth) acrylate, the methylene bis (meth) acrylamide, the (meth) acrylamide methylene ether, and the condensate of polyhydric alcohol and N-methylol (meth) acrylamide Mono Or the like triacrylate formal. These polyfunctional monomers can be used individually or in combination of 2 or more types.

It is preferable that it is 1 mass% or more and 30 mass% or less with respect to solid content of the photosensitive composition of a 1st aspect, and, as for content of a photopolymerizable compound (A2), it is more preferable that it is 5 mass% or more and 20 mass% or less. By setting it as said range, there exists a tendency which is easy to obtain the balance of sensitivity, developability, and resolution.

It does not specifically limit as a photoinitiator (C) in the photosensitive composition of a 1st aspect, A conventionally well-known photoinitiator can be used.

Specifically as a photoinitiator (C), 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) Phenyl] -2-hydroxy-2-methyl-1-propane-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dode Silphenyl) -2-hydroxy-2-methylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethan-1-one, bis (4-dimethylaminophenyl) ketone, 2-methyl -1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl], 1- (O-acetyloxime), (9-ethyl-6-nitro-9H-carbox Bazol-3-yl) [4- (2-methoxy-1-methylethoxy) -2-methylphenyl] methanone O-acetyloxime, 2- (benzoyloxyimino) -1- [4- (phenylthio) Phenyl] -1-octanone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 4-benzoyl-4'-methyldimethylsulfide, 4-dimethylaminobenzoic acid, 4-dimethyl Methyl aminobenzoate, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 4-dimethylamino-2-ethylhexylbenzoic acid, 4-dimethylamino-2-isoamylbenzoic acid, benzyl-β-methoxyethylacetal, benzyl Dimethyl ketal, 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) oxime, methyl o-benzoylbenzoate, 2,4-diethyl thioxanthone, 2-chlorothioxanthone, 2 , 4-dimethyl thioxanthone, 1-chloro-4-propoxy city oxanthone, thioxanthene, 2-chlorothioxanthene, 2,4-diethylthioxanthene, 2-methylthioxanthene, 2- Isopropyl thioxanthene, 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, azobisisobutyronitrile, benzoylperoxide, cumene hydroperoxide, 2-mercaptobenzoimidazole, 2-mercaptobenzooxazole, 2-mercaptobenzothiazole, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) -imidazolyl 2 Monomer, benzophenone, 2-chlorobenzophenone, p, p'-bisdi Methylaminobenzophenone, 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, benzyl, benzoin, benzoin methyl ether, benzo Inethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, benzoin butyl ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylamino Propiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone, p-dimethylaminoacetophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, α, α -Dichloro-4-phenoxyacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropyl thioxanthone, dibenzosveron, pentyl-4-dimethylaminobenzoate, 9-phenylacridine, 1,7-bis- (9-acridinyl) heptane, 1,5-bis- (9-acridinyl) pentane, 1,3-bis- (9-acridinyl) propane, p-methoxytri Gin, 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [2- (5-methylfuran -2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4,6-bis (trichloromethyl ) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3 , 4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s- Triazine, 2- (4-ethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4,6-bis (trichloro Methyl) -s-triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4-methoxy) phenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2-bromo-4-methoxy) phenyl-s-triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4-methoxy) styrylphenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2- Homes-4-methoxy) styryl phenyl -s- triazine, and the like. These photoinitiators can be used individually or in combination of 2 or more types.

Among these, using an oxime system photoinitiator is especially preferable at the point of a sensitivity. Among the oxime photoinitiators, particularly preferred are O-acetyl-1- [6- (2-methylbenzoyl) -9-ethyl-9H-carbazol-3-yl] ethanone oxime, ethanone, 1- [9-ethyl-6- (pyrrole-2-ylcarbonyl) -9H-carbazol-3-yl], 1- (O-acetyloxime) and 1,2-octanedione, 1- [4- (phenyl Thio)-, 2- (O-benzoyloxime)].

As a photoinitiator, it is also preferable to use the oxime type compound represented by following formula (c1).

[Formula 29]

(R ^c1 is a group selected from the group consisting of monovalent organic groups, amino groups, halogens, nitro groups and cyano groups,

n1 is an integer of 0 or more and 4 or less,

n2 is 0 or 1,

R ^c2 is a phenyl group which may have a substituent or a carbazolyl group which may have a substituent,

R ^c3 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)

In formula (c1), R <^c1> is not specifically limited in the range which does not inhibit the objective of this invention, It is suitably selected from various organic groups. Suitable examples when R ^c1 is an organic group include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, a saturated aliphatic acyloxy group, an alkoxycarbonyl group, a phenyl group which may have a substituent, and a phenoxy which may have a substituent The time period, the benzoyl group which may have a substituent, the phenoxycarbonyl group which may have a substituent, the benzoyloxy group which may have a substituent, the phenylalkyl group which may have a substituent, the naphthyl group which may have a substituent, and the naph which may have a substituent A methoxy group, the naphthoyl group which may have a substituent, the naphthoxycarbonyl group which may have a substituent, the naphthoyloxy group which may have a substituent, the naphthylalkyl group which may have a substituent, the heterocyclyl group which may have a substituent, and an amino group Amino, morpholin-1-yl, and piperazin-1-yl groups substituted with 1 or 2 organic groups, halogen, nitro groups, and cyano groups Etc. can be mentioned. When n1 is an integer of 2 or more and 4 or less, R <^c1> may be same or different. In addition, the carbon atom number of a substituent does not contain the carbon atom number of the substituent which a substituent further has.

When R <^c1> is an alkyl group, ^C1- C20 is preferable and ^C1-C6 is more preferable. Moreover, when R <^c1> is an alkyl group, linear or branched chain may be sufficient as it. As a specific example when R <^c1> is an alkyl group, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert- butyl group, n-pentyl group, iso Pentyl group, sec-pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group, isononyl group, n-decyl group, isodecyl group, etc. are mentioned. Moreover, when R ^c1 is an alkyl group, the alkyl group may contain the ether bond (-O-) in a carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include methoxyethyl group, ethoxyethyl group, methoxyethoxyethyl group, ethoxyethoxyethyl group, propyloxyethoxyethyl group and methoxypropyl group.

When R <^c1> is an alkoxy group, ^C1- C20 is preferable and ^C1-C6 is more preferable. Moreover, when R <^c1> is an alkoxy group, linear or branched chain may be sufficient as it. As a specific example when R <^c1> is an alkoxy group, a methoxy group, an ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, sec-butyloxy group, tert- butyl jade Period, n-pentyloxy group, isopentyloxy group, sec-pentyloxy group, tert-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, isooctyloxy group, sec-octane A tiloxy group, tert-octyloxy group, n-nonyloxy group, isononyloxy group, n-decyloxy group, isodecyloxy group, etc. are mentioned. Moreover, when R <^c1> is an alkoxy group, the alkoxy group may contain the ether bond (-O-) in a carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include methoxyethoxy group, ethoxyethoxy group, methoxyethoxyethoxy group, ethoxyethoxyethoxy group, propyloxyethoxyethoxy group and methoxy A oxypropyloxy group etc. are mentioned.

When R <^c1> is a cycloalkyl group or a cycloalkoxy group, C3 or more and 10 or less are preferable, and C3 or more and 6 or less are more preferable. As a specific example when R <^c1> is a cycloalkyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, etc. are mentioned. As a specific example when R <^c1> is a cycloalkoxy group, a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, a cyclooctyloxy group, etc. are mentioned.

When R <^c1> is saturated aliphatic acyl group or saturated aliphatic acyloxy group, ^C2 or more and 20 or less are preferable, and ^C2 or more and 7 or less are more preferable. Specific examples when R ^c1 is a saturated aliphatic acyl group include an acetyl group, propanoyl group, n-butanoyl group, 2-methylpropanoyl group, n-pentanoyl group, 2,2-dimethylpropanoyl group, n-hexa Noyl group, n-heptanoyl group, n-octanoyl group, n-nonanoyl group, n-decanoyl group, n-undecanoyl group, n-dodecanoyl group, n-tridecanoyl group, n- tetradecanoyl group, n-pentadecanoyl group, n-hexadecanoyl group, etc. are mentioned. As a specific example when R <^c1> is a saturated aliphatic acyloxy group, an acetyloxy group, a propanoyloxy group, n-butanoyloxy group, 2-methylpropanoyloxy group, n-pentanoyloxy group, 2,2-dimethylpro Panoyloxy group, n-hexanoyloxy group, n-heptanoyloxy group, n-octanoyloxy group, n-nonanoyloxy group, n-decanoyloxy group, n-undecanoyloxy group, n-dodecanoyloxy group , n-tridecanoyloxy group, n-tetradecanoyloxy group, n-pentadecanoyloxy group, n-hexadecanoyloxy group, and the like.

When R <^c1> is an alkoxycarbonyl group, ^C2 or more and 20 or less are preferable, and ^C2 or more and 7 or less are more preferable. As a specific example when R <^c1> is an alkoxycarbonyl group, a methoxycarbonyl group, an ethoxycarbonyl group, n-propyloxycarbonyl group, isopropyloxycarbonyl group, n-butyloxycarbonyl group, isobutyloxycarbonyl group, sec-butyloxycarbonyl group, tert -Butyloxycarbonyl group, n-pentyloxycarbonyl group, isopentyloxycarbonyl group, sec-pentyloxycarbonyl group, tert-pentyloxycarbonyl group, n-hexyloxycarbonyl group, n-heptyloxycarbonyl group, n-octyloxycarbonyl group, isooctyloxycarbonyl group , sec-octyloxylcarbonyl group, tert-octyloxycarbonyl group, n-nonyloxycarbonyl group, isononyloxycarbonyl group, n-decyloxycarbonyl group, isodecyloxycarbonyl group, and the like.

When R <^c1> is a phenylalkyl group, C7 or more and 20 or less are preferable, and C7 or more and 10 or less are more preferable. Moreover, when R <^c1> is a naphthyl alkyl group, C11 or more and 20 or less are preferable, and C11 or more and 14 or less are more preferable. As a specific example when R <^c1> is a phenylalkyl group, a benzyl group, 2-phenylethyl group, 3-phenylpropyl group, and 4-phenylbutyl group are mentioned. Specific examples in the case where R ^c1 is a naphthylalkyl group include α-naphthylmethyl group, β-naphthylmethyl group, 2- (α-naphthyl) ethyl group and 2- (β-naphthyl) ethyl group. When R ^c1 is a phenylalkyl group or a naphthylalkyl group, R ^c1 may further have a substituent on the phenyl group or naphthyl group.

When R ^c1 is a heterocyclyl group, the heterocyclyl group is a 5- or 6-membered monocyclic ring containing one or more N, S, O, or a heterocyclyl group in which these monocycles or condensed monocyclic and benzene rings are condensed. In the case where the heterocyclyl group is a condensed ring, it is assumed to have a ring number of up to three. The heterocycles constituting such heterocyclyl groups include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyri Midine, pyridazine, benzofuran, benzothiophene, indole, isoindole, indolizine, benzoimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, fructose Tallazine, cinnoline, quinoxaline, etc. are mentioned. When R ^c1 is a heterocyclyl group, the heterocyclyl group may further have a substituent.

When R ^c1 is an amino group substituted with 1 or 2 organic groups, suitable examples of the organic group include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and 2 to 20 carbon atoms Saturated aliphatic acyl group, phenyl group which may have a substituent, benzoyl group which may have a substituent, C7-C20 or more phenylalkyl group which may have a substituent, naphthyl group which may have a substituent, and a substituent may have The naphthyl group, the naphthyl alkyl group, the heterocyclyl group, etc. which have 11 to 20 carbon atoms which may have a substituent are mentioned. Specific examples of such suitable organic ^groups are the same as those of R ^c1 . Specific examples of the amino group substituted with 1 or 2 organic groups include methylamino group, ethylamino group, diethylamino group, n-propylamino group, di-n-propylamino group, isopropylamino group, n-butylamino group, di-n- Butylamino group, n-pentylamino group, n-hexylamino group, n-heptylamino group, n-octylamino group, n-nonylamino group, n-decylamino group, phenylamino group, naphthylamino group, acetylamino group, propanoylamino group, n- Butanoylamino group, n-pentanoylamino group, n-hexanoylamino group, n-heptanoylamino group, n-octanoylamino group, n-decanoylamino group, benzoylamino group, α-naphthoylamino group and β-naphthoylamino group Can be mentioned.

As a substituent in the case where a phenyl group, a naphthyl group, and heterocyclyl group contained in R <^c1> have a substituent further, a C1-C6 alkyl group, a C1-C6 alkoxy group, carbon number of carbon atoms Monoalkylamino group having a saturated aliphatic acyl group having 2 to 7 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic acyloxy group having 2 to 7 carbon atoms, an alkyl group having 1 to 6 carbon atoms, And dialkylamino groups, morpholin-1-yl groups, piperazin-1-yl groups, halogens, nitro groups, and cyano groups having an alkyl group having 1 to 6 carbon atoms. When the phenyl group, naphthyl group and heterocyclyl group contained in R ^c1 further have a substituent, the number of the substituents is not limited within the range not impairing the object of the present invention, but is preferably 1 or more and 4 or less. When the phenyl group, naphthyl group, and heterocyclyl group contained in R ^c1 have a plurality of substituents, the plurality of substituents may be the same or different.

In R <^c1> , since it is chemically stable, there are few steric hindrances, and the synthesis | combination of an oxime ester compound is easy, etc., C1-C6 alkyl group, C1-C6 alkoxy group, And A group selected from the group consisting of saturated aliphatic acyl groups having 2 to 7 carbon atoms is preferable, alkyl having 1 to 6 carbon atoms is more preferable, and a methyl group is particularly preferable.

R ^c1 is the position is a phenyl group that is R ^c1 bond binding to the phenyl group, the position of the coupling hand of the main skeleton of the phenyl group and the oxime ester compound in the case of the position of the methyl group in the 1-position and 2-position, 4-position or 5-position is preferable, and 5-position is more preferable. Moreover, the integer of 0 or more and 3 or less is preferable, as for n1, the integer of 0 or more and 2 or less is more preferable, and 0 or 1 is especially preferable.

R ^c2 is a phenyl group which may have a substituent or a carbazolyl group which may have a substituent. In addition, when R ^c2 is a carbazolyl group which may have a substituent, the nitrogen atom on the carbazolyl group may be substituted with an alkyl group having 1 to 6 carbon atoms.

In ^Rc2 , the substituent which a phenyl group or carbazolyl group has is not specifically limited in the range which does not inhibit the objective of this invention. Examples of suitable substituents in which a phenyl group or carbazolyl group may have on a carbon atom include an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and a cycloalkyl having 3 to 10 carbon atoms. Alkyl group, C3-C10 cycloalkoxy group, C2-C20 saturated aliphatic acyl group, C2-C20 alkoxycarbonyl group, C2-C20 saturated aliphatic acyl The time period, the phenyl group which may have a substituent, the phenoxy group which may have a substituent, the phenylthio group which may have a substituent, the benzoyl group which may have a substituent, the phenoxycarbonyl group which may have a substituent, and the benzoyl jade which may have a substituent A phenylalkyl group having 7 to 20 carbon atoms, a naphthyl group which may have a substituent, a naphthoxy group which may have a substituent, A naphthoyl group which may have a substituent, a naphthoxycarbonyl group which may have a substituent, a naphthoyloxy group which may have a substituent, a naphthylalkyl group having 11 to 20 carbon atoms which may have a substituent, or a substituent Heterocyclyl group, a heterocyclylcarbonyl group which may have a substituent, an amino group, the amino group substituted by the 1 or 2 organic group, the morpholin-1-yl group, the piperazin-1-yl group, a halogen, a nitro group, a cyano group, etc. Can be mentioned.

When R ^c2 is a carbazolyl group, examples of suitable substituents in which the carbazolyl group may have on the nitrogen atom include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and carbon atoms A saturated aliphatic acyl group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, a phenyl group which may have a substituent, a benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, and a substituent may have A phenylalkyl group having 7 to 20 carbon atoms, a naphthyl group which may have a substituent, a naphthoyl group which may have a substituent, a naphthoxycarbonyl group which may have a substituent, and 11 to 20 carbon atoms that may have a substituent. A naphthyl alkyl group, the heterocyclyl group which may have a substituent, the heterocyclyl carbonyl group which may have a substituent, etc. are mentioned. Among these substituents, an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, and an ethyl group is particularly preferable.

In the specific example of the substituent which a phenyl group or carbazolyl group may have, an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, an alkoxycarbonyl group, a saturated aliphatic acyloxy group, the phenylalkyl group which may have a substituent, The naphthylalkyl group which may have a substituent, the heterocyclyl group which may have a substituent, and the amino group substituted by 1 or 2 organic groups are the same as R <^c1> .

Examples of the substituent in the case of R ^c2 in which the phenyl group, naphthyl group and heterocyclyl group contained in the substituent having a phenyl group or carbazolyl group further have a substituent include an alkyl group having 1 to 6 carbon atoms; An alkoxy group having 1 to 6 carbon atoms; Saturated aliphatic acyl groups having 2 to 7 carbon atoms; An alkoxycarbonyl group having 2 to 7 carbon atoms; Saturated aliphatic acyloxy group having 2 to 7 carbon atoms; Phenyl group; Naphthyl group; Benzoyl group; Naphthoyl group; Benzoyl group substituted by a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, and a phenyl group; Monoalkylamino groups having an alkyl group having 1 to 6 carbon atoms; Dialkylamino group having an alkyl group having 1 to 6 carbon atoms; Morpholin-1 -yl group; Piperazin-1-yl group; halogen; Nitro group; Cyano group is mentioned. When the phenyl group, naphthyl group and heterocyclyl group contained in the substituent which a phenyl group or carbazolyl group have further a substituent, the number of the substituent is not limited in the range which does not impair the objective of this invention, but is 1 or more 4 The following is preferable. When the phenyl group, naphthyl group and heterocyclyl group have a plurality of substituents, the plurality of substituents may be the same or different.

In R <^c2> , group represented by the following formula (c2) or (c3) is preferable from the point which is easy to obtain the photoinitiator excellent in the sensitivity, group represented by the following formula (c2) is more preferable, and following formula (c2) As the group represented by, a group in which A is S is particularly preferable.

[Formula 30]

(R ^c4 is a group selected from the group consisting of monovalent organic groups, amino groups, halogens, nitro groups and cyano groups, A is S or O, and n3 is an integer of 0 or more and 4 or less.)

[Formula 31]

(R ^c5 and R ^c6 are each monovalent organic group.)

When R ^c4 in Formula (c2) is an organic group, it can select from various organic groups in the range which does not impair the objective of this invention. In the formula (c2), suitable examples in the case where R ^c4 is an organic group include an alkyl group having 1 to 6 carbon atoms; An alkoxy group having 1 to 6 carbon atoms; Saturated aliphatic acyl groups having 2 to 7 carbon atoms; An alkoxycarbonyl group having 2 to 7 carbon atoms; Saturated aliphatic acyloxy group having 2 to 7 carbon atoms; Phenyl group; Naphthyl group; Benzoyl group; Naphthoyl group; Benzoyl group substituted by a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, and a phenyl group; Monoalkylamino groups having an alkyl group having 1 to 6 carbon atoms; Dialkylamino group having an alkyl group having 1 to 6 carbon atoms; Morpholin-1 -yl group; Piperazin-1-yl group; halogen; Nitro group; Cyano group is mentioned.

In R <^c4> , a benzoyl group; Naphthoyl group; Benzoyl group substituted by a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, and a phenyl group; Nitro group is preferable and a benzoyl group; Naphthoyl group; 2-methylphenylcarbonyl group; 4- (piperazin-1-yl) phenylcarbonyl group; 4- (phenyl) phenylcarbonyl group is more preferable.

In formula (c2), n3 is preferably an integer of 0 or more and 3 or less, more preferably an integer of 0 or more and 2 or less, and particularly preferably 0 or 1. if n3 is 1, the binding position of R ^c4 is a phenyl group which is bonded R ^c4 in the coupling hand to combine with an oxygen atom or a sulfur atom, a para-position is preferred.

R ^c5 in Formula (c3) can be selected from various organic groups in the range which does not impair the objective of this invention. Preferred examples of R ^c5 include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a saturated aliphatic acyl group having 2 to 20 carbon atoms, and an alkoxy having 2 to 20 carbon atoms. A carbonyl group, a phenyl group which may have a substituent, a benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a phenylalkyl group having 7 to 20 carbon atoms which may have a substituent, a naphthyl group which may have a substituent, A naphthoyl group which may have a substituent, a naphthoxycarbonyl group which may have a substituent, a naphthylalkyl group which has 11 to 20 carbon atoms which may have a substituent, a heterocyclyl group which may have a substituent, and a substituent may have Heterocyclyl carbonyl group etc. are mentioned.

In R ^c5 , an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, and an ethyl group is particularly preferable.

R ^c6 in Formula (c3) is not specifically limited in the range which does not impair the objective of this invention, It can select from various organic groups. As a specific example of group suitable as R <^c6> , C1-C20 alkyl group, the phenyl group which may have a substituent, the naphthyl group which may have a substituent, and the heterocyclyl group which may have a substituent are mentioned. As R <^c6> , in these groups, the phenyl group which may have a substituent is more preferable, and 2-methylphenyl group is especially preferable.

As a substituent in the case where a phenyl group, a naphthyl group, and a heterocyclyl group contained in R <^c4> , R <^c5> or R <^c6> have a substituent further, they are a C1- ^C6 alkyl group, C1- ^C6 or less Alkoxy group, C2-C7 saturated aliphatic acyl group, C2-C7 alkoxycarbonyl group, C2-C7 saturated aliphatic acyloxy group, C1-C6 alkyl group And monoalkylamino groups having a dialkylamino group, dialkylamino groups having 1 to 6 carbon atoms, morpholin-1-yl groups, piperazin-1-yl groups, halogens, nitro groups and cyano groups. When the phenyl group, naphthyl group and heterocyclyl group contained in R ^c4 , R ^c5 or R ^c6 further have a substituent, the number of the substituents is not limited within a range not impairing the object of the present invention, but at least one. 4 or less is preferable. When the phenyl group, naphthyl group, and heterocyclyl group contained in R ^c4 , R ^c5 or R ^c6 have a plurality of substituents, the plurality of substituents may be the same or different.

R ^c3 in Formula (c1) is a hydrogen atom or an alkyl group of 1 to 6 carbon atoms. As R <^c3> , a methyl group or an ethyl group is preferable and a methyl group is more preferable.

Among the oxime ester compounds represented by the formula (c1), the following PI-1 to PI-42 may be mentioned as particularly suitable compounds.

[Formula 32]

[Formula 33]

[Formula 34]

[Formula 35]

[Formula 36]

[Formula 37]

Moreover, the oxime ester compound represented by following formula (c4) is also preferable as a photoinitiator.

[Formula 38]

(R ^c7 is a hydrogen atom, a nitro group or a monovalent organic group, R ^c8 and R ^c9 are each a chain alkyl group which may have a substituent, a cyclic organic group which may have a substituent or a hydrogen atom, and R ^c8 and R ^c9 are May combine with each other to form a ring; R ^c10 is a monovalent organic group, R ^c11 is a hydrogen atom, an alkyl group having 1 to 11 carbon atoms which may have a substituent, or an aryl group which may have a substituent, n4 Is an integer of 0 or more and 4 or less, and n5 is 0 or 1.)

Here, as an oxime compound for manufacturing the oxime ester compound of a formula (c4), the compound represented by a following formula (c5) is suitable.

[Formula 39]

(R ^c7 , R ^c8 , R ^c9 , R ^c10 , n4 and n5 are the same as in the formula (c4).)

In formulas (c4) and (c5), R ^c7 is a hydrogen atom, a nitro group or a monovalent organic group. R ^c7 is bonded to a 6-membered aromatic ring different from the 6-membered aromatic ring bonded to the group represented _by- (CO) _n5 -on the fluorene ring in the formula (c4). In formula (c4), the bonding position with respect to the fluorene ring of ^Rc7 is not specifically limited. Coupled to formula (c4), when a compound represented by having at least one R ^c7, equation (c4) from the 2- position such as will facilitate the synthesis of the compound, one of the at least one of R ^c7 fluorene ring represented by It is desirable to. When there are a plurality of R ^c7 , a plurality of R ^c7 may be the same or different.

When ^Rc7 is an organic group, ^Rc7 is not specifically limited in the range which does not impair the objective of this invention, It is suitably selected from various organic groups. Suitable examples when R ^c7 is an organic group include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, a saturated aliphatic acyloxy group, an alkoxycarbonyl group, a phenyl group which may have a substituent, and a phenoxy which may have a substituent The time period, the benzoyl group which may have a substituent, the phenoxycarbonyl group which may have a substituent, the benzoyloxy group which may have a substituent, the phenylalkyl group which may have a substituent, the naphthyl group which may have a substituent, and the naph which may have a substituent Methoxy group, naphthoyl group which may have a substituent, naphthoxycarbonyl group which may have a substituent, naphthoyloxy group which may have a substituent, naphthylalkyl group which may have a substituent, heterocyclyl group which may have a substituent, and a substituent Heterocyclylcarbonyl group, an amino group substituted with 1 or 2 organic groups, morpholin-1-yl group and piperazine-1 -Diary etc. are mentioned.

When R <^c7> is an alkyl group, 1 or more and 20 or less are preferable and, as for the carbon atom number of an alkyl group, 1 or more and 6 or less are more preferable. Moreover, when R <^c7> is an alkyl group, linear or branched chain may be sufficient as it. As a specific example when ^Rc7 is an alkyl group, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, iso Pentyl group, sec-pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group, isononyl group, n-decyl group, isodecyl group, etc. are mentioned. Moreover, when R ^c7 is an alkyl group, the alkyl group may contain the ether bond (-O-) in a carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include methoxyethyl group, ethoxyethyl group, methoxyethoxyethyl group, ethoxyethoxyethyl group, propyloxyethoxyethyl group and methoxypropyl group.

When R <^c7> is an alkoxy group, 1 or more and 20 or less are preferable and, as for the carbon atom number of an alkoxy group, 1 or more and 6 or less are more preferable. Moreover, when R <^c7> is an alkoxy group, linear or branched chain may be sufficient as it. As a specific example when ^Rc7 is an alkoxy group, a methoxy group, an ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, sec-butyloxy group, tert- butyl jade Period, n-pentyloxy group, isopentyloxy group, sec-pentyloxy group, tert-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, isooctyloxy group, sec-octane A tiloxy group, tert-octyloxy group, n-nonyloxy group, isononyloxy group, n-decyloxy group, isodecyloxy group, etc. are mentioned. Moreover, when R ^c7 is an alkoxy group, the alkoxy group may contain the ether bond (-O-) in a carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include methoxyethoxy group, ethoxyethoxy group, methoxyethoxyethoxy group, ethoxyethoxyethoxy group, propyloxyethoxyethoxy group and methoxy A oxypropyloxy group etc. are mentioned.

When R ^c7 is a cycloalkyl group or a cycloalkoxy group, 3 or more and 10 or less are preferable and, as for carbon number of a cycloalkyl group or a cycloalkoxy group, 3 or more and 6 or less are more preferable. As a specific example when R <^c7> is a cycloalkyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, etc. are mentioned. Specific examples in the case where R ^c7 is a cycloalkoxy group include cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy group, cyclohexyloxy group, cycloheptyloxy group, cyclooctyloxy group and the like.

When ^Rc7 is a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, 2 or more and 21 or less are preferable and, as for carbon number of a saturated aliphatic acyl group or saturated aliphatic acyloxy group, 2 or more and 7 or less are more preferable. Specific examples when R ^c7 is a saturated aliphatic acyl group include an acetyl group, propanoyl group, n-butanoyl group, 2-methylpropanoyl group, n-pentanoyl group, 2,2-dimethylpropanoyl group, n-hexa Noyl group, n-heptanoyl group, n-octanoyl group, n-nonanoyl group, n-decanoyl group, n-undecanoyl group, n-dodecanoyl group, n-tridecanoyl group, n- tetradecanoyl group, n-pentadecanoyl group, n-hexadecanoyl group, etc. are mentioned. As a specific example when R <^c7> is a saturated aliphatic acyloxy group, an acetyloxy group, a propanoyloxy group, n-butanoyloxy group, 2-methyl propanoyloxy group, n-pentanoyloxy group, 2,2-dimethylpro Panoyloxy group, n-hexanoyloxy group, n-heptanoyloxy group, n-octanoyloxy group, n-nonanoyloxy group, n-decanoyloxy group, n-undecanoyloxy group, n-dodecanoyloxy group , n-tridecanoyloxy group, n-tetradecanoyloxy group, n-pentadecanoyloxy group, n-hexadecanoyloxy group, and the like.

When ^Rc7 is an alkoxycarbonyl group, 2 or more and 20 or less are preferable and, as for the carbon atom number of an alkoxycarbonyl group, 2 or more and 7 or less are more preferable. As a specific example when ^Rc7 is an alkoxycarbonyl group, a methoxycarbonyl group, an ethoxycarbonyl group, n-propyloxycarbonyl group, isopropyloxycarbonyl group, n-butyloxycarbonyl group, isobutyloxycarbonyl group, sec-butyloxycarbonyl group, tert -Butyloxycarbonyl group, n-pentyloxycarbonyl group, isopentyloxycarbonyl group, sec-pentyloxycarbonyl group, tert-pentyloxycarbonyl group, n-hexyloxycarbonyl group, n-heptyloxycarbonyl group, n-octyloxycarbonyl group, isooctyloxycarbonyl group , sec-octyloxycarbonyl group, tert-octyloxycarbonyl group, n-nonyloxycarbonyl group, isononyloxycarbonyl group, n-decyloxycarbonyl group, isodecyloxycarbonyl group, and the like.

When R <^c7> is a phenylalkyl group, 7 or more and 20 or less are preferable, and, as for the carbon number of a phenylalkyl group, 7 or more and 10 or less are more preferable. Moreover, when R <^c7> is a naphthyl alkyl group, 11 or more and 20 or less are preferable and, as for the carbon number of a naphthyl alkyl group, 11 or more and 14 or less are more preferable. As a specific example when R <^c7> is a phenylalkyl group, a benzyl group, 2-phenylethyl group, 3-phenylpropyl group, and 4-phenylbutyl group are mentioned. Specific examples in the case where R ^c7 is a naphthylalkyl group include α-naphthylmethyl group, β-naphthylmethyl group, 2- (α-naphthyl) ethyl group and 2- (β-naphthyl) ethyl group. In the case where R ^c7 is a phenylalkyl group or a naphthylalkyl group, R ^c7 may further have a substituent on the phenyl group or naphthyl group.

When R ^c7 is a heterocyclyl group, the heterocyclyl group is a 5- or 6-membered monocyclic ring containing one or more N, S, O or these monocyclic rings or a heterocyclyl group in which the monocyclic and benzene rings are condensed. In the case where the heterocyclyl group is a condensed ring, it is assumed to have a ring number of up to three. The heterocyclyl group may be either an aromatic group (heteroaryl group) or a non-aromatic group. Examples of heterocycles constituting such heterocyclyl groups include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, Pyrimidine, pyridazine, benzofuran, benzothiophene, indole, isoindole, indolizine, benzoimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, Phthalazine, cinnoline, quinoxaline, piperidine, piperazine, morpholine, piperidine, tetrahydropyran, tetrahydrofuran and the like. When R ^c7 is a heterocyclyl group, the heterocyclyl group may further have a substituent.

When R ^c7 is a heterocyclylcarbonyl group, the heterocyclyl group contained in the heterocyclylcarbonyl group is the same as when R ^c7 is a heterocyclyl group.

When R ^c7 is an amino group substituted with 1 or 2 organic groups, suitable examples of the organic group include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and 2 to 21 carbon atoms Saturated aliphatic acyl group, phenyl group which may have a substituent, benzoyl group which may have a substituent, C7-C20 or more phenylalkyl group which may have a substituent, naphthyl group which may have a substituent, and a substituent may have The naphthyl group, the naphthyl alkyl group, the heterocyclyl group, etc. which have 11 to 20 carbon atoms which may have a substituent are mentioned. Specific examples of these suitable organic ^groups are the same as those of R ^c7 . Specific examples of the amino group substituted with 1 or 2 organic groups include methylamino group, ethylamino group, diethylamino group, n-propylamino group, di-n-propylamino group, isopropylamino group, n-butylamino group, di-n- Butylamino group, n-pentylamino group, n-hexylamino group, n-heptylamino group, n-octylamino group, n-nonylamino group, n-decylamino group, phenylamino group, naphthylamino group, acetylamino group, propanoylamino group, n- Butanoylamino group, n-pentanoylamino group, n-hexanoylamino group, n-heptanoylamino group, n-octanoylamino group, n-decanoylamino group, benzoylamino group, α-naphthoylamino group and β-naphthoylamino group Can be mentioned.

As a substituent in the case where a phenyl group, a naphthyl group, and heterocyclyl group contained in R <^c7> have a substituent further, a C1-C6 alkyl group, a C1-C6 alkoxy group, carbon number of carbon atoms Monoalkylamino group having a saturated aliphatic acyl group having 2 to 7 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic acyloxy group having 2 to 7 carbon atoms, an alkyl group having 1 to 6 carbon atoms, And dialkylamino groups, morpholin-1-yl groups, piperazin-1-yl groups, halogens, nitro groups, and cyano groups having an alkyl group having 1 to 6 carbon atoms. When the phenyl group, naphthyl group, and heterocyclyl group contained in R ^c7 further have a substituent, the number of the substituents is not limited within the range not impairing the object of the present invention, but is preferably 1 or more and 4 or less. When the phenyl group, naphthyl group, and heterocyclyl group contained in R ^c7 have a plurality of substituents, the plurality of substituents may be the same or different.

Among the groups described above, R ^c7 is preferably a group represented by a nitro group or R ^c12 -CO- because the sensitivity tends to be improved. R <^c12> is not specifically limited in the range which does not impair the objective of this invention, It can select from various organic groups. Examples of the group suitable as R ^c12 include an alkyl group having 1 to 20 carbon atoms, a phenyl group which may have a substituent, a naphthyl group which may have a substituent, and a heterocyclyl group which may have a substituent. Among these groups as R ^c12 , 2-methylphenyl group, thiophen-2-yl group and α-naphthyl group are particularly preferable.

Moreover, since ^Rc7 is a hydrogen atom, there exists a tendency for transparency to become favorable, and it is preferable. Moreover, when R <^c7> is a hydrogen atom and R <^c10> is group represented by Formula (c4a) or (c4b) mentioned later, transparency tends to become more favorable.

In formula (c4), R <^c8> and R <^c9> are linear alkyl groups which may have a substituent, cyclic organic group which may have a substituent, or a hydrogen atom, respectively. R ^c8 and R ^c9 may be bonded to each other to form a ring. Among these groups, a chain alkyl group which may have a substituent as R ^c8 and R ^c9 is preferable. When R <^c8> and R <^c9> are linear alkyl groups which may have a substituent, a linear alkyl group may be a linear alkyl group or a branched alkyl group may be sufficient as it.

When R <^c8> and R <^c9> are linear alkyl groups which do not have a substituent, 1 or more and 20 or less are preferable, as for carbon number of a chain alkyl group, 1 or more and 10 or less are more preferable, 1 or more and 6 or less are especially preferable. As a specific example when R <^c8> and R <^c9> are linear alkyl groups, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert- butyl group, n- Pentyl group, isopentyl group, sec-pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group, Isononyl group, n-decyl group, isodecyl group, etc. are mentioned. In addition, when ^Rc8 and ^Rc9 are alkyl groups, the alkyl group may contain the ether bond (-O-) in a carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include methoxyethyl group, ethoxyethyl group, methoxyethoxyethyl group, ethoxyethoxyethyl group, propyloxyethoxyethyl group and methoxypropyl group.

When ^Rc8 and ^Rc9 are linear alkyl groups which have a substituent, 1 or more and 20 or less are preferable, as for carbon number of a chain alkyl group, 1 or more and 10 or less are more preferable, 1 or more and 6 or less are especially preferable. In this case, the number of carbon atoms of the substituent is not included in the number of carbon atoms of the chain alkyl group. It is preferable that the linear alkyl group which has a substituent is linear.

The substituent which an alkyl group may have is not specifically limited in the range which does not inhibit the objective of this invention. Suitable examples of the substituent include cyano group, halogen atom, cyclic organic group and alkoxycarbonyl group. As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned. In these, a fluorine atom, a chlorine atom, and a bromine atom are preferable. Cycloalkyl group, aromatic hydrocarbon group, heterocyclyl group is mentioned as cyclic organic group. As a specific example of a cycloalkyl group, it is the same as the suitable example in case R <^c7> is a cycloalkyl group. As a specific example of an aromatic hydrocarbon group, a phenyl group, a naphthyl group, a biphenylyl group, an anthryl group, a phenanthryl group, etc. are mentioned. Specific examples of the heterocyclyl group are the same as those in the case where R ^c7 is a heterocyclyl group. When R ^c7 is an alkoxycarbonyl group, the alkoxy group contained in the alkoxycarbonyl group may be linear or branched, and linear is preferable. 1 or more and 10 or less are preferable and, as for the carbon atom number of the alkoxy group contained in an alkoxycarbonyl group, 1 or more and 6 or less are more preferable.

When the chain alkyl group has a substituent, the number of substituents is not particularly limited. Preferred number of substituents vary depending on the number of carbon atoms of the chain alkyl group. The number of substituents is typically 1 or more and 20 or less, 1 or more and 10 or less are preferable, and 1 or more and 6 or less are more preferable.

When ^Rc8 and ^Rc9 are cyclic organic groups, an cyclic organic group may be an alicyclic group or an aromatic group may be sufficient as it. Examples of the cyclic organic group include aliphatic cyclic hydrocarbon groups, aromatic hydrocarbon groups, and heterocyclyl groups. When R ^c8 and R ^c9 are cyclic organic groups, the substituent which the cyclic organic group may have is the same as when R ^c8 and R ^c9 are chain alkyl groups.

In the case where R ^c8 and R ^c9 are aromatic hydrocarbon groups, the aromatic hydrocarbon group is preferably a phenyl group, a group formed by bonding of a plurality of benzene rings through a carbon-carbon bond, or a group formed by condensation of a plurality of benzene rings. When the aromatic hydrocarbon group is a phenyl group or a group formed by bonding or condensation of a plurality of benzene rings, the number of rings of the benzene ring contained in the aromatic hydrocarbon group is not particularly limited, 3 or less is preferable, 2 or less is more preferable, and 1 is particularly preferable. Do. As a preferable specific example of an aromatic hydrocarbon group, a phenyl group, a naphthyl group, a biphenylyl group, an anthryl group, a phenanthryl group, etc. are mentioned.

When R ^c8 and R ^c9 are aliphatic cyclic hydrocarbon groups, the aliphatic cyclic hydrocarbon group may be monocyclic or polycyclic. Although the number of carbon atoms of an aliphatic cyclic hydrocarbon group is not specifically limited, 3 or more and 20 or less are preferable and 3 or more and 10 or less are more preferable. Examples of the monocyclic cyclic hydrocarbon group include a cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, norbornyl group, isobornyl group, tricyclononyl group and tricyclode A real group, a tetracyclo dodecyl group, an adamantyl group, etc. are mentioned.

When R ^c8 and R ^c9 are heterocyclyl groups, the heterocyclyl group is a 5- or 6-membered monocyclic ring containing one or more N, S, O, or a heterocyclyl group condensed with such monocyclic rings or benzene rings to be. In the case where the heterocyclyl group is a condensed ring, it is assumed to have a ring number of up to three. The heterocyclyl group may be either an aromatic group (heteroaryl group) or a non-aromatic group. Examples of heterocycles constituting such heterocyclyl groups include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, Pyrimidine, pyridazine, benzofuran, benzothiophene, indole, isoindole, indolizine, benzoimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, Phthalazine, cinnoline, quinoxaline, piperidine, piperazine, morpholine, piperidine, tetrahydropyran, tetrahydrofuran and the like.

R ^c8 and R ^c9 may be bonded to each other to form a ring. It is preferable that the group which consists of the ring which ^Rc8 and ^Rc9 form is a cycloalkylidene group. When R <^c8> and R <^c9> combine and form a cycloalkylidene group, it is preferable that the ring which comprises a cycloalkylidene group is a 5-membered ring-a 6-membered ring, and it is more preferable that it is a 5-membered ring.

When the group formed by the bonding of ^Rc8 and ^Rc9 is a cycloalkylidene group, the cycloalkylidene group may be condensed with one or more other rings. Examples of the ring that may be condensed with a cycloalkylidene group include a benzene ring, a naphthalene ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a furan ring, a thiophene ring, a pyrrole ring and a pyridine ring And pyrazine ring and pyrimidine ring.

Examples of suitable groups among R ^c8 and R ^c9 described above include groups represented by the formula -A ¹ -A ² . In formula, A <^1> is a linear alkylene group and A <^2> is an alkoxy group, a cyano group, a halogen atom, a halogenated alkyl group, a cyclic organic group, or an alkoxycarbonyl group.

1 or more and 10 or less are preferable and, as for the carbon atom number of A <^1> linear alkylene group, 1 or more and 6 or less are more preferable. In the case where A ² is an alkoxy group, the alkoxy group may be linear or branched, and linear is preferable. 1 or more and 10 or less are preferable and, as for the carbon atom number of an alkoxy group, 1 or more and 6 or less are more preferable. When A <^2> is a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are preferable, and a fluorine atom, a chlorine atom, and a bromine atom are more preferable. When A ² is a halogenated alkyl group, the halogen atom contained in the halogenated alkyl group is preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and more preferably a fluorine atom, a chlorine atom or a bromine atom. The halogenated alkyl group may be linear or branched, and linear is preferable. When A <^2> is a cyclic organic group, the example of a cyclic organic group is the same as that of the cyclic organic group which ^Rc8 and ^Rc9 have as a substituent. When A <^2> is an alkoxycarbonyl group, the example of the alkoxycarbonyl group is the same as the alkoxycarbonyl group which R <^c8> and R <^c9> have as a substituent.

Suitable specific examples of R ^c8 and R ^c9 include alkyl groups such as ethyl group, n-propyl group, n-butyl group, n-hexyl group, n-heptyl group and n-octyl group; 2-methoxyethyl group, 3-methoxy-n-propyl group, 4-methoxy-n-butyl group, 5-methoxy-n-pentyl group, 6-methoxy-n-hexyl group, 7-methoxy -n-heptyl group, 8-methoxy-n-octyl group, 2-ethoxyethyl group, 3-ethoxy-n-propyl group, 4-ethoxy-n-butyl group, 5-ethoxy-n-pen Alkoxyalkyl groups such as a methyl group, 6-ethoxy-n-hexyl group, 7-ethoxy-n-heptyl group and 8-ethoxy-n-octyl group; 2-cyanoethyl group, 3-cyano-n-propyl group, 4-cyano-n-butyl group, 5-cyano-n-pentyl group, 6-cyano-n-hexyl group, 7-cyano cyanoalkyl groups such as -n-heptyl group and 8-cyano-n-octyl group; 2-phenylethyl group, 3-phenyl-n-propyl group, 4-phenyl-n-butyl group, 5-phenyl-n-pentyl group, 6-phenyl-n-hexyl group, 7-phenyl-n-heptyl group and Phenylalkyl groups such as 8-phenyl-n-octyl group; 2-cyclohexylethyl group, 3-cyclohexyl-n-propyl group, 4-cyclohexyl-n-butyl group, 5-cyclohexyl-n-pentyl group, 6-cyclohexyl-n-hexyl group, 7-cyclohexyl -n-heptyl group, 8-cyclohexyl-n-octyl group, 2-cyclopentylethyl group, 3-cyclopentyl-n-propyl group, 4-cyclopentyl-n-butyl group, 5-cyclopentyl-n-pen Cycloalkylalkyl groups such as a methyl group, 6-cyclopentyl-n-hexyl group, 7-cyclopentyl-n-heptyl group, and 8-cyclopentyl-n-octyl group; 2-methoxycarbonylethyl group, 3-methoxycarbonyl-n-propyl group, 4-methoxycarbonyl-n-butyl group, 5-methoxycarbonyl-n-pentyl group, 6-methoxycarbonyl -n-hexyl group, 7-methoxycarbonyl-n-heptyl group, 8-methoxycarbonyl-n-octyl group, 2-ethoxycarbonylethyl group, 3-ethoxycarbonyl-n-propyl group, 4-ethoxycarbonyl-n-butyl group, 5-ethoxycarbonyl-n-pentyl group, 6-ethoxycarbonyl-n-hexyl group, 7-ethoxycarbonyl-n-heptyl group and 8- Alkoxycarbonylalkyl groups such as ethoxycarbonyl-n-octyl group; 2-chloroethyl group, 3-chloro-n-propyl group, 4-chloro-n-butyl group, 5-chloro-n-pentyl group, 6-chloro-n-hexyl group, 7-chloro-n-heptyl group, 8-chloro-n-octyl group, 2-bromoethyl group, 3-bromo-n-propyl group, 4-bromo-n-butyl group, 5-bromo-n-pentyl group, 6-bromo- n-hexyl group, 7-bromo-n-heptyl group, 8-bromo-n-octyl group, 3,3,3-trifluoropropyl group and 3,3,4,4,5,5,5 And halogenated alkyl groups such as -heptafluoro-n-pentyl group.

Among the above suitable groups as R ^c8 and R ^c9 are ethyl group, n-propyl group, n-butyl group, n-pentyl group, 2-methoxyethyl group, 2-cyanoethyl group, 2-phenylethyl group, 2-cyclohexylethyl group, 2-methoxycarbonylethyl group, 2-chloroethyl group, 2-bromoethyl group, 3,3,3-trifluoropropyl group and 3,3,4,4,5,5,5-heptafluoro-n It is a pentyl group.

Examples of suitable organic groups for R ^c10 are, like R ^c7 , an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, an alkoxycarbonyl group, a saturated aliphatic acyloxy group, a phenyl group which may have a substituent, a substituent A phenoxy group which may have, a benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a benzoyloxy group which may have a substituent, a phenylalkyl group which may have a substituent, a naphthyl group which may have a substituent, a substituent Naphthoxy group which may have a substituent, naphthoyl group which may have a substituent, naphthoxycarbonyl group which may have a substituent, naphthoyloxy group which may have a substituent, naphthylalkyl group which may have a substituent, and a substituent may have Heterocyclyl group, heterocyclylcarbonyl group which may have a substituent, amino group substituted by 1 or 2 organic groups, morpholin-1-yl group, and Piperazin-1-yl group etc. are mentioned. Specific examples of these groups are the same as those described for R ^c7 . Moreover, as R <^c10> , a cycloalkylalkyl group, the phenoxyalkyl group which may have a substituent on an aromatic ring, and the phenylthioalkyl group which may have a substituent on an aromatic ring are preferable. The substituent which the phenoxyalkyl group and the phenylthioalkyl group may have is the same as the substituent which the phenyl group contained in R <^c7> may have.

Among the organic groups, R ^c10 is preferably an alkyl group, a cycloalkyl group, a phenyl group which may have a substituent or a cycloalkylalkyl group, or a phenylthioalkyl group which may have a substituent on an aromatic ring. As the alkyl group, an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 8 carbon atoms is more preferable, an alkyl group having 1 to 4 carbon atoms is particularly preferable, and a methyl group is most preferred. . In the phenyl group which may have a substituent, a methylphenyl group is preferable and 2-methylphenyl group is more preferable. 5 or more and 10 or less are preferable, as for carbon number of the cycloalkyl group contained in a cycloalkyl alkyl group, 5 or more and 8 or less are more preferable, 5 or 6 is especially preferable. 1-8 or more are preferable, as for carbon number of the alkylene group contained in a cycloalkylalkyl group, 1 or more and 4 or less are more preferable, and 2 is especially preferable. In a cycloalkylalkyl group, a cyclopentyl ethyl group is preferable. 1-8 are preferable, as for carbon number of the alkylene group contained in the phenylthioalkyl group which may have a substituent on an aromatic ring, 1 or more and 4 or less are more preferable, and 2 is especially preferable. Among the phenylthioalkyl groups which may have a substituent on the aromatic ring, 2- (4-chlorophenylthio) ethyl group is preferable.

The roneun R ^c10, it is preferable airway represented by -A ³ -CO-OA ^4. A ³ is a divalent organic group, preferably a divalent hydrocarbon group, and preferably an alkylene group. A ⁴ is a monovalent organic group, and preferably a monovalent hydrocarbon group.

In the case where A ³ is an alkylene group, the alkylene group may be linear or branched, and linear is preferable. When A <^3> is an alkylene group, 1 or more and 10 or less are preferable, as for carbon number of an alkylene group, 1 or more and 6 or less are more preferable, and 1 or more and 4 or less are especially preferable.

Suitable examples of A ⁴ include an alkyl group having 1 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and an aromatic hydrocarbon group having 6 to 20 carbon atoms. Suitable specific examples of A ⁴ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group , Phenyl group, naphthyl group, benzyl group, phenethyl group, α-naphthylmethyl group and β-naphthylmethyl group.

Suitable specific examples of the group represented by -A ³ -CO-OA ⁴ include 2-methoxycarbonylethyl group, 2-ethoxycarbonylethyl group, 2-n-propyloxycarbonylethyl group, 2-n-butyl Oxycarbonylethyl group, 2-n-pentyloxycarbonylethyl group, 2-n-hexyloxycarbonylethyl group, 2-benzyloxycarbonylethyl group, 2-phenoxycarbonylethyl group, 3-methoxycarbonyl-n -Propyl group, 3-ethoxycarbonyl-n-propyl group, 3-n-propyloxycarbonyl-n-propyl group, 3-n-butyloxycarbonyl-n-propyl group, 3-n-pentyloxy Carbonyl-n-propyl group, 3-n-hexyloxycarbonyl-n-propyl group, 3-benzyloxycarbonyl-n-propyl group, 3-phenoxycarbonyl-n-propyl group, etc. are mentioned. have.

Above has been described with respect to R ^c10, R ^c10 is preferably a group represented by the following formula (c4a) or (c4b) roneun.

[Formula 40]

(Formula (c4a) and (c4b) and of, R ^c13 and R ^c14 are each an organic group, n6 is an integer of not less than 0 4, R ^c13 and R ^c14 are when present in adjacent positions on the benzene ring, R ^c13 and ^Rc14 may combine with each other to form a ring, n7 is an integer of 1 or less and 8 or less, n8 is an integer of 1 or more and 5 or less, n9 is an integer of 0 or more (n8 + 3) and R ^c15 is It is an organic group.)

^Examples of the organic ^group for R ^c13 and R ^c14 in the formula (c4a) are the same as those for R ^c7 . As R <^c13> , an alkyl group or a phenyl group is preferable. When R <^c13> is an alkyl group, the carbon atom number is 1 or less, 10 or more are preferable, 1 or more and 5 or less are more preferable, 1 or more and 3 or less are especially preferable, and 1 is the most preferable. That is, R ^c13 is most preferably a methyl group. When R <^c13> and R <^c14> combine and form a ring, the said ring may be an aromatic ring or an aliphatic ring may be sufficient as it. As a group represented by a formula (c4a), the suitable example of the group in which R ^{< c13>} and R <^c14> forms a ring is a naphthalen-1-yl group, a 1,2,3,4- tetrahydro naphthalene-5-yl group, etc. Can be mentioned. In said formula (c4a), n6 is an integer of 0 or more and 4 or less, It is preferable that it is 0 or 1, It is more preferable that it is 0.

In the formula (c4b), R ^c15 is an organic group. As an organic group, the group similar to the organic group demonstrated about R <^c7> is mentioned. In an organic group, an alkyl group is preferable. The alkyl group may be linear or branched. 1 or more and 10 or less are preferable, as for the carbon atom number of an alkyl group, 1 or more and 5 or less are more preferable, and 1 or more and 3 or less are especially preferable. As R <^c15> , a methyl group, an ethyl group, a propyl group, isopropyl group, a butyl group, etc. are illustrated preferably, Among these, it is more preferable that it is a methyl group.

In said formula (c4b), n8 is an integer of 1 or more and 5 or less, the integer of 1 or more and 3 or less is preferable, and 1 or 2 is more preferable. In said formula (c4b), n9 is 0 or more (n8 + 3) or less, the integer of 0 or more and 3 or less is preferable, the integer of 0 or more and 2 or less is more preferable, and 0 is especially preferable. In said formula (c4b), n7 is an integer of 1-8, an integer of 1-5 is preferable, the integer of 1-3 is more preferable, 1 or 2 is especially preferable.

In formula (c4), R <^c11> is a hydrogen atom, the C1-C11 alkyl group which may have a substituent, or the aryl group which may have a substituent. As a substituent which you may have when R <^c11> is an alkyl group, a phenyl group, a naphthyl group, etc. are mentioned preferably. Moreover, as a substituent which you may have when R <^c7> is an aryl group, C1-C5 alkyl group, an alkoxy group, a halogen atom, etc. are illustrated preferably.

In formula (c4), as ^Rc11 , a hydrogen atom, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, a phenyl group, benzyl group, methylphenyl group, naphthyl group, etc. are illustrated preferably, Among these, , Methyl group or phenyl group is more preferable.

The compound represented by formula (c4) converts an oxime group (> C = N-OH) contained in the compound represented by formula (c5) described above to an oxime ester group represented by> C = NO-COR ^c11 . It is manufactured by the method of containing. R ^c11 and R ^c11 are the same as in the formula (c4).

The conversion of an oxime group (> C = N-OH) to an oxime ester group represented by> C = NO-COR ^c11 is performed by reacting an acylating agent with a compound represented by the above formula (c5).

With an acylating agent to give an acyl group represented by -COR ^c11 is, (R ^c11 CO), an acid anhydride or, R ^c11 COHal represented by ₂ O may be mentioned an acid halide represented by (Hal represents a halogen atom).

As a suitable specific example of a compound represented by a formula (c4), the following PI-43-PI-83 are mentioned.

[Formula 41]

[Formula 42]

It is preferable that content of a photoinitiator is 0.5 mass part or more and 20 mass parts or less with respect to 100 mass parts of solid content of the photosensitive composition of a 1st aspect. By setting it as said range, sufficient heat resistance and chemical-resistance can be obtained, a coating film formation ability can be improved, and a hardening defect can be suppressed.

The photosensitive composition of a 1st aspect contains a hydrogen barrier agent (B) as above. When this compound is contained in the photosensitive composition, pattern formation which has a hydrogen barrier performance is attained.

It is preferable that it is 0.5 mass part or more and 95 mass parts or less with respect to 100 mass parts of said photoinitiators, and, as for content of a hydrogen barrier agent (B), it is more preferable that they are 1 mass part or more and 50 mass parts or less. By setting it as said range, the hydrogen barrier film excellent in hydrogen barrier property can be formed, and favorable fine patterning characteristic can be acquired, while obtaining favorable developability.

The photosensitive composition of a 1st aspect may contain the coloring agent further. By containing a coloring agent, it is used suitably as a color filter formation use of image display apparatuses, such as a liquid crystal display display and an organic electroluminescent display, for example. Moreover, the photosensitive composition of a 1st aspect is used suitably as a black matrix formation use in a color filter, for example by including a light shielding agent as a coloring agent.

Although it does not specifically limit as a coloring agent, For example, The compound classified as pigment in the color index (CI; The Society of Dyers and Colourists), Specifically, the following color index (CI) It is preferable to use the numbered pigment.

C.I. Pigment Yellow 1 (hereinafter, "CI Pigment Yellow" is the same and describes only the numbers.), 3, 11, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 55, 60, 61, 65, 71, 73, 74, 81, 83, 86, 93, 95, 97, 98, 99, 100, 101, 104, 106, 108, 109, 110, 113, 114, 116, 117, 119, 120, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 166, 167, 168, 175, 180, 185;

C.I. Pigment Orange 1 (Hereinafter, "CI Pigment Orange" is the same and describes only a number.), 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 55, 59, 61, 63, 64, 71, 73;

C.I. Pigment Violet 1 (hereinafter, "C.I. Pigment Violet" is the same and describes only the numbers.), 19, 23, 29, 30, 32, 36, 37, 38, 39, 40, 50;

C.I. Pigment Red 1 (hereinafter, "CI Pigment Red" is the same and describes only the numbers.), 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48: 1, 48: 2, 48: 3, 48: 4, 49: 1, 49: 2, 50: 1, 52: 1, 53: 1, 57, 57: 1, 57: 2, 58: 2, 58: 4, 60: 1, 63: 1, 63: 2, 64: 1, 81: 1, 83, 88, 90: 1, 97, 101, 102, 104, 105, 106, 108, 112, 113, 114, 122, 123, 144, 146, 149, 150, 151, 155, 166, 168, 170, 171, 172, 174, 175, 176, 177, 178, 179, 180, 185, 187, 188, 190, 192, 193, 194, 202, 206, 207, 208, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 242, 243, 245, 254, 255, 264, 265;

C.I. Pigment Blue 1 (hereinafter, "C.I. Pigment Blue" is the same and describes only numbers), 2, 15, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66;

C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. Pigment green 37;

C.I. Pigment Brown 23, C.I. Pigment Brown 25, C.I. Pigment Brown 26, C.I. Pigment brown 28;

C.I. Pigment Black 1, C.I. Pigment Black 7.

Moreover, when using a coloring agent as a light shielding agent, it is preferable to use a black pigment as a light shielding agent. As the black pigment, organic matters such as carbon oxides, metal oxides such as carbon black, titanium black, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, silver, complex oxides, metal sulfides, metal sulfates, and metal carbonates are used. Regardless, various pigments may be mentioned. Among these, it is preferable to use carbon black which has high light-shielding property.

As carbon black, although well-known carbon black, such as channel black, furnace black, thermal black, and lamp black, can be used, it is preferable to use channel black which is excellent in light-shielding property. Moreover, you may use resin coating carbon black.

Since resin-coated carbon black has lower electrical conductivity than carbon black without resin coating, when used as a black matrix of a liquid crystal display, there is little leakage of current, and it is possible to manufacture a display of high power consumption with high reliability.

Moreover, in order to adjust the color tone of carbon black, you may add said organic pigment suitably as an auxiliary pigment.

Moreover, in order to disperse | distribute a coloring agent uniformly in the photosensitive composition, you may use a dispersing agent further. As such a dispersing agent, it is preferable to use the polymer dispersing agent of a polyethyleneimine system, a urethane resin system, and an acrylic resin system. In particular, when carbon black is used as the colorant, it is preferable to use an acrylic resin dispersant as the dispersant.

In addition, although an inorganic pigment and an organic pigment may respectively be used independently and may be used together, when using together, 10 mass parts or more and 80 mass parts or less of an organic pigment with respect to 100 mass parts of total amounts of an inorganic pigment and an organic pigment are used together. It is preferable to use in the range of, and it is more preferable to use in the range of 20 mass parts or more and 40 mass parts or less.

Although what is necessary is just to determine content of a coloring agent suitably according to the use of the photosensitive composition of a 1st aspect, 5 mass parts or more and 70 mass parts or less are preferable with respect to 100 mass parts of solid content of the photosensitive composition of a 1st aspect, 25 The mass part or more and 60 mass parts or less are more preferable.

When forming a black matrix especially using the photosensitive composition of a 1st aspect, it is preferable to adjust the quantity of the light-shielding agent in a photosensitive composition so that the OD value per 1 micrometer of film thicknesses of a black matrix may be four or more. . When the OD value per film thickness of 1 micrometer in a black matrix is four or more, when using for the black matrix of a liquid crystal display, sufficient display contrast can be obtained.

Moreover, it is preferable to add a coloring agent to the photosensitive composition, after setting it as the dispersion liquid disperse | distributed to the suitable density | concentration using a dispersing agent.

As an organic solvent in the photosensitive composition of a 1st aspect, For example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol Monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether , Propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, di Propylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl (Poly) alkylene glycol monoalkyl ether, such as hotel and the like; (Poly) alkylenes such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate Glycol monoalkyl ether acetates; Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether and tetrahydrofuran; Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone; Lactic acid alkyl esters such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate; Ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2 Methyl hydroxy-3-methylbutyrate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-acetic acid- Butyl, isobutyl acetate, n-pentyl formate, isopentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, acetoacetic acid Other esters such as methyl, ethyl acetoacetate, and ethyl 2-iodobutane; Aromatic hydrocarbons such as toluene and xylene; And amides such as N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, and a solvent represented by the formula (a04). These organic solvents can be used individually or in combination of 2 or more types.

Among the above organic solvents, propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 3 Amides, such as -methoxybutyl acetate, N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, and the solvent represented by said formula (a04), are alkali-soluble resin (A1). ) And the photopolymerizable compound (A2), the photopolymerization initiator (C) and the hydrogen barrier agent (B) are preferred because they exhibit excellent solubility.

The content of the organic solvent is preferably in an amount of 1% by mass or more and 50% by mass or less, and more preferably in an amount of 5% by mass or more and 30% by mass or less.

(2) the photosensitive composition of the second aspect

The photosensitive composition of the second aspect is a positive photosensitive composition. In the case where the photosensitive composition of the second aspect is a chemically amplified positive photosensitive composition, the action of an acid generator (hereinafter also referred to as a photoacid generator) and an acid generating an acid by irradiation with active light or radiation It contains resin (so-called photosensitive resin hereinafter) which increases solubility in alkali. The photosensitive composition may contain components, such as alkali-soluble resin, an acid diffusion inhibitor, an organic solvent, as needed. As a photosensitive composition of another 2nd aspect, positive type photosensitive composition containing quinonediazide group containing compound and alkali-soluble resin (for example, novolak resin (C1) etc. which are mentioned later), such as a quinone diazide group containing compound Can be mentioned.

The film thickness of the resist pattern formed using the photosensitive composition of a 2nd aspect is not specifically limited. The photosensitive composition of a 2nd aspect is used suitably for formation of the resist pattern of a thick film. Although the film thickness of the resist pattern formed using the photosensitive composition of a 2nd aspect is not specifically limited, Specifically, 0.1 micrometer or more is preferable, 1 micrometer or more and 150 micrometers or less are more preferable, 10 micrometers or more and 120 Particularly preferred is not more than m, and particularly preferably not less than 20 m and not more than 80 m.

Hereinafter, the essential or arbitrary component which the photosensitive composition of a 2nd aspect contains, and the manufacturing method of the photosensitive composition are demonstrated.

A photo-acid generator is a compound which generate | occur | produces an acid by irradiation of actinic light or a radiation, and will not specifically limit, if it is a compound which generate | occur | produces an acid directly or indirectly by light.

Hereinafter, the suitable example of the photo-acid generator used suitably in the photosensitive composition of a 2nd aspect is demonstrated.

As a 1st example of a suitable photo-acid generator, the compound represented by a following formula (a1) is mentioned.

[Formula 43]

In said formula (a1), X <^1a> represents the sulfur atom or iodine atom of valence g, and g is 1 or 2. h represents the number of repeat units of the structure in parentheses. R ^1a is an organic group bonded to X ^1a , an aryl group having 6 to 30 carbon atoms, a heterocyclic group having 4 to 30 carbon atoms, an alkyl group having 1 to 30 carbon atoms, and 2 carbon atoms Or more represent 30 or less alkenyl group or 2 or more and 30 or less alkynyl group, R ^1a represents alkyl, hydroxy, alkoxy, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, arylthiocarbon Each group of carbonyl, acyloxy, arylthio, alkylthio, aryl, heterocycle, aryloxy, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, alkyleneoxy, amino, cyano, nitro, and It may be substituted by at least 1 sort (s) chosen from the group which consists of halogen. The number of R ^1a is g + h (g-1) +1, and R <^1a> may mutually be same or different, respectively. In addition, two or more R ^1a directly to each other, or _{-O-, -S-, -SO-, -SO 2} -, -NH-, -NR 2a -, -CO-, -COO-, -CONH-, A ring structure containing X ^1a may be formed by bonding through an alkylene group having 1 to 3 carbon atoms or a phenylene group. R ^2a is an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 10 carbon atoms.

X ^2a is a structure represented by the following formula (a2).

[Formula 44]

In the formula (a2), X ^4a represents a divalent group of an alkylene group having 1 to 8 carbon atoms, an allylene group having 6 to 20 carbon atoms, or a heterocyclic compound having 8 to 20 carbon atoms, and X ^4a is selected from the group consisting of alkyl having 1 to 8 carbon atoms, alkoxy having 1 to 8 carbon atoms, aryl, hydroxy, cyano and nitro having 6 to 10 carbon atoms, and halogen. At least 1 type may be substituted. X ^5a is —O—, —S—, —SO—, —SO ₂ —, —NH—, —NR ^2a —, —CO—, —COO—, —CONH—, alkyl having 1 to 3 carbon atoms A lene group or a phenylene group is represented. h represents the number of repeat units of the structure in parentheses. h + 1 ^X4a and ^hX5a may be same or different, respectively. R ^2a is the same as defined above.

X ^3a- it may include a borate anion represented by the phosphate anion or the formula (a18) a fluorinated alkyl-fluoro represented by a counter ion of onium, the formula (a17).

[Formula 45]

In said formula (a17), R <^3a> represents the alkyl group in which 80% or more of hydrogen atoms were substituted by the fluorine atom. j represents the number and is an integer of 1 or more and 5 or less. j pieces of R ^3a may be the same or different, respectively.

[Formula 46]

In the formula (a18), R ^4a to R ^7a each independently represent a fluorine atom or a phenyl group, and part or all of the hydrogen atoms of the phenyl group are at least one member selected from the group consisting of fluorine atoms and trifluoromethyl groups. It may be substituted.

Examples of the onium ions in the compound represented by the formula (a1) include triphenylsulfonium, tri-p-tolylsulfonium, 4- (phenylthio) phenyldiphenylsulfonium, and bis [4- (diphenylsulfonio ) Phenyl] sulfide, bis [4- {bis [4- (2-hydroxyethoxy) phenyl] sulfonio} phenyl] sulfide, bis [4- [bis (4-fluorophenyl) sulfonio ] Phenyl] sulfide, 4- (4-benzoyl-2-chlorophenylthio) phenylbis (4-fluorophenyl) sulfonium, 7-isopropyl-9-iodo-10-thia-9,10-di Hydroanthracene-2-yldi-p-tolylsulfonium, 7-isopropyl-9-iodo-10-thia-9,10-dihydroanthracene-2-yldiphenylsulfonium, 2-[(diphenyl) sul Phenio] thioxanthone, 4- [4- (4-tert-butylbenzoyl) phenylthio] phenyldi-p-tolylsulfonium, 4- (4-benzoylphenylthio) phenyldiphenylsulfonium, diphenylphena Silsulfonium, 4-hydroxyphenylmethylbenzylsulfonium, 2-naphthylmethyl (1-ethoxycarbonyl) ethylsulfonium, 4-hydroxyphenylmethylphenacylsulfonium, phenyl [4- (4- ratio Nylthio) phenyl] 4-biphenylsulfonium, phenyl [4- (4-biphenylthio) phenyl] 3-biphenylsulfonium, [4- (4-acetphenylthio) phenyl] diphenylsulfonium, octa Decylmethylphenacylsulfonium, diphenyl iodonium, di-p-tolyl iodonium, bis (4-dodecylphenyl) iodonium, bis (4-methoxyphenyl) iodonium, (4-octyloxyphenyl) phenyl iodo Nium, bis (4-decyloxy) phenylyodonium, 4- (2-hydroxytetradecyloxy) phenylphenylyodonium, 4-isopropylphenyl (p-tolyl) iodonium or 4-isobutylphenyl ( p-tolyl) iodonium, etc. are mentioned.

Among the onium ions in the compound represented by the formula (a1), preferred sulfonium ions include the sulfonium ions represented by the following formula (a19).

[Formula 47]

In said formula (a19), R <^8a> is respectively independently a hydrogen atom, alkyl, hydroxy, alkoxy, alkylcarbonyl, alkylcarbonyloxy, alkyloxycarbonyl, a halogen atom, aryl which may have a substituent, and arylcarbonyl Group selected from the group consisting of: X ^2a have the same meanings as X ^2a in the formula (a1).

As a specific example of the sulfonium ion represented by said formula (a19), 4- (phenylthio) phenyl diphenyl sulfonium and 4- (4-benzoyl-2- chlorophenylthio) phenyl bis (4-fluorophenyl) ) Sulfonium, 4- (4-benzoyl phenylthio) phenyldiphenylsulfonium, phenyl [4- (4-biphenylthio) phenyl] 4-biphenylsulfonium, phenyl [4- (4-biphenylthio) Phenyl] 3-biphenylsulfonium, [4- (4-acetphenylthio) phenyl] diphenylsulfonium, and diphenyl [4- (p-terphenylthio) phenyl] diphenylsulfonium.

In the fluorinated alkyl fluorophosphate anion represented by the formula (a17), R ^3a represents an alkyl group substituted with a fluorine atom, and the number of preferred carbon atoms is 1 or more and 8 or less, and more preferably 1 or more and 4 or less. Specific examples of the alkyl group include straight chain alkyl groups such as methyl, ethyl, propyl, butyl, pentyl and octyl; Branched alkyl groups such as isopropyl, isobutyl, sec-butyl and tert-butyl; Furthermore, cycloalkyl groups, such as cyclopropyl, cyclobutyl, cyclopentyl, a cyclhexyl, etc. are mentioned, The ratio in which the hydrogen atom of the alkyl group was substituted by the fluorine atom is 80% or more normally, Preferably it is 90% or more, More preferably, Is 100%. When the substitution rate of a fluorine atom is less than 80%, the acid strength of the onium fluorinated alkyl fluorophosphate represented by the formula (a1) decreases.

Particularly preferred R ^3a is a linear or branched perfluoroalkyl group having 1 to 4 carbon atoms and a substitution rate of 100% of fluorine atoms. Specific examples include CF ₃ , CF ₃ CF ₂ , and (CF ₃ ) _2. CF, CF ₃ CF ₂ CF ₂ , CF ₃ CF ₂ CF ₂ CF ₂ , (CF ₃ ) ₂ CFCF ₂ , CF ₃ CF ₂ (CF ₃ ) CF, (CF ₃ ) ₃ C. The number j of R ^3a is an integer of 1 or more and 5 or less, Preferably it is 2 or more and 4 or less, Especially preferably, it is 2 or 3.

Specific examples of the preferred fluorinated alkylfluorophosphate anion include [(CF ₃ CF ₂ ) ₂ PF ₄ ] ^- , [(CF ₃ CF ₂ ) ₃ PF ₃ ] ^- , [((CF ₃ ) ₂ CF) ₂ PF ₄ ] ^- , [((CF ₃ ) ₂ CF) ₃ PF ₃ ] ^- , [(CF ₃ CF ₂ CF ₂ ) ₂ PF ₄ ] ^- , [(CF ₃ CF ₂ CF ₂ ) ₃ PF ₃ ] ^- , [ _{((CF 3) 2 CFCF 2} ) 2 PF 4] -, [((CF 3) 2 CFCF 2) 3 PF 3] -, [(CF 3 CF 2 CF 2 CF 2) 2 PF 4] - or [( CF ₃ CF ₂ CF ₂ ) ₃ PF ₃ ] ^- , among these, [(CF ₃ CF ₂ ) ₃ PF ₃ ] ^- , [(CF ₃ CF ₂ CF ₂ ) ₃ PF ₃ ] ^- , [( _{(CF 3) 2 CF) 3} PF 3] -, [((CF 3) 2 CF) 2 PF 4] -, [((CF 3) 2 CFCF 2) 3 PF 3] - or [((CF _{3) 2 CFCF 2) 2 PF 4]} - are particularly preferred.

Preferable specific examples of the borate anion represented by the formula (a18) include tetrakis (pentafluorophenyl) borate ([B (C ₆ F ₅ ) ₄ ] ^- ), tetrakis ((trifluoromethyl) phenyl ] Borate ([B (C ₆ H ₄ CF ₃ ) ₄ ] ^- ), difluorobis (pentafluorophenyl) borate ([(C ₆ F ₅ ) ₂ BF ₂ ] ^- ), trifluoro (pentafluoro Rophenyl) borate ([(C ₆ F ₅ ) BF ₃ ] ^- ), tetrakis (difluorophenyl) borate ([B (C ₆ H ₃ F ₂ ) ₄ ] ^- ), and the like. Among these, tetrakis (pentafluorophenyl) borate ([B (C ₆ F ₅ ) ₄ ] ^- ) is particularly preferable.

Second examples of suitable photoacid generators are 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (2-furyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methyl-2-furyl) ethenyl] -s-triazine , 2,4-bis (trichloromethyl) -6- [2- (5-ethyl-2-furyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- [2 -(5-propyl-2-furyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,5-dimethoxyphenyl) ethenyl] -s- Triazine, 2,4-bis (trichloromethyl) -6- [2- (3,5-diethoxyphenyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,5-dipropoxyphenyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- [2- (3-methoxy-5-ethoxyphenyl) Ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- [2- (3-methoxy-5-propoxyphenyl) ethenyl] -s-triazine, 2,4- Bis (trichloromethyl) -6- [2- (3,4-methylenedioxyphenyl) ethenyl ] -s-triazine, 2,4-bis (trichloromethyl) -6- (3,4-methylenedioxyphenyl) -s-triazine, 2,4-bis-trichloromethyl-6- (3 -Bromo-4-methoxy) phenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2-bromo-4-methoxy) phenyl-s-triazine, 2,4- Bis-trichloromethyl-6- (2-bromo-4-methoxy) styrylphenyl-s-triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4-methoxy ) Styrylphenyl-s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2- (2-furyl) ethenyl] -4,6-bis (trichloromethyl) -1,3, 5-triazine, 2- [2- (5-methyl-2-furyl) ethenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2- (3 , 5-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4 , 6-bis (trichloromethyl) -1,3,5-triazine, 2- (3,4-methylenedioxyphenyl) -4,6- Bis (trichloromethyl) -1,3,5-triazine, tris (1,3-dibromopropyl) -1,3,5-triazine, tris (2,3-dibromopropyl) -1 And halogen-containing triazine compounds represented by the following formula (a3) such as halogen-containing triazine compounds such as 3,5-triazine and tris (2,3-dibromopropyl) isocyanurate.

[Formula 48]

In said formula (a3), R <^9a> , R <^10a> , and R <^11a> represent a halogenated alkyl group each independently.

Third examples of suitable photoacid generators include α- (p-toluenesulfonyloxyimino) -phenylacetonitrile, α- (benzenesulfonyloxyimino) -2,4-dichlorophenylacetonitrile, α- (benzene Sulfonyloxyimino) -2,6-dichlorophenylacetonitrile, α- (2-chlorobenzenesulfonyloxyimino) -4-methoxyphenylacetonitrile, α- (ethylsulfonyloxyimino) -1-cyclophene The compound represented by following formula (a4) containing a tenyl acetonitrile and an oxime sulfonate group is mentioned.

[Formula 49]

In said formula (a4), R <^12a> represents monovalent, divalent, or trivalent organic group, R <^13a> represents a substituted or unsubstituted saturated hydrocarbon group, an unsaturated hydrocarbon group, or an aromatic compound group, n represents the structure of a parenthesis Indicates the number of repeat units.

In said formula (a4), an aromatic compound group represents group of the compound which shows the physical / chemical property peculiar to an aromatic compound, For example, aryl groups, such as a phenyl group and a naphthyl group, and heteroaryl groups, such as a furyl group and thienyl group, are mentioned. Can be. These may have one or more suitable substituents, for example, a halogen atom, an alkyl group, an alkoxy group, a nitro group, etc. on a ring. In addition, R ^13a is particularly preferably an alkyl group having 1 to 6 carbon atoms, and includes a methyl group, an ethyl group, a propyl group, and a butyl group. In particular, a compound in which R ^12a is an aromatic compound group and R ^13a is an alkyl group having 1 to 4 carbon atoms are preferable.

As a photo-acid generator represented by said formula (a4), when n = 1, R <^12a> is either a phenyl group, a methylphenyl group, or a methoxyphenyl group, and R <^13a> is a compound, specifically alpha (methylsul) Ponyloxyimino) -1-phenylacetonitrile, α- (methylsulfonyloxyimino) -1- (p-methylphenyl) acetonitrile, α- (methylsulfonyloxyimino) -1- (p-methoxyphenyl) Acetonitrile, [2- (propylsulfonyloxyimino) -2,3-dihydroxythiophen-3-ylidene] (o-tolyl) acetonitrile, etc. are mentioned. When n = 2, as a photo-acid generator represented by said formula (a4), the photo-acid generator represented by a following formula is mentioned specifically ,.

[Formula 50]

As a 4th example in a suitable photo-acid generator, the onium salt which has a naphthalene ring in a cation part is mentioned. This "having a naphthalene ring" means having a structure derived from naphthalene, and means that the structure of at least two rings and such aromaticity are maintained. This naphthalene ring may have substituents, such as a C1-C6 linear or branched alkyl group, a hydroxyl group, and a C1-C6 linear or branched alkoxy group. Although the structure derived from a naphthalene ring may be monovalent (one free valence is 1) or divalent (two free valences) may be sufficient, it is preferable that it is monovalent (however, the part which couple | bonds with the said substituent at this time is The free valences are excluded). As for the number of naphthalene rings, 1 or more and 3 or less are preferable.

As a cation part of the onium salt which has a naphthalene ring in such a cation part, the structure represented by following formula (a5) is preferable.

[Formula 51]

In said formula (a5), at least 1 of R <^14a> , R <^15a> , and R <^16a> represents group represented by following formula (a6), and the remainder is a linear or branched alkyl group of 1 to 6 carbon atoms, or a substituent. The phenyl group, hydroxyl group, or C1-C6 linear or branched alkoxy group which may have is shown. Alternatively, one of R ^14a , R ^15a and R ^16a is a group represented by the following formula (a6), and the other two are each independently a linear or branched alkylene group having 1 to 6 carbon atoms, and these terminals This combination may be annular.

[Formula 52]

In said formula (a6), R <^17a> , R <^18a> respectively independently represents a hydroxyl group, a C1-C6 linear or branched alkoxy group, or a C1-C6 linear or branched alkyl group. , R ^19a represents a linear or branched alkylene group having 1 to 6 carbon atoms which may have a single bond or a substituent. l and m respectively independently represent the integer of 0 or more and 2 or less, and l + m is 3 or less. However, when two or more R <^17a> exists, they may mutually be same or different. In addition, when two or more R <^18a> exists, they may mutually be same or different.

The number of groups represented by the formula (a6) in the R ^14a , R ^15a , and R ^16a is preferably one from the point of stability of the compound, and the remainder is linear or branched having 1 to 6 carbon atoms. It is an alkylene group of phase, These terminal may couple | bond and may be cyclic. In this case, the two alkylene groups constitute a 3 to 9 membered ring including a sulfur atom. The number of atoms (including sulfur atoms) constituting the ring is preferably 5 or more and 6 or less.

Moreover, as a substituent which the said alkylene group may have, an oxygen atom (in this case, a carbonyl group is formed with the carbon atom which comprises an alkylene group), a hydroxyl group, etc. are mentioned.

Examples of the substituent which the phenyl group may have include a hydroxyl group, a linear or branched alkoxy group having 1 to 6 carbon atoms, a linear or branched alkyl group having 1 to 6 carbon atoms, and the like.

Suitable examples of these cationic moieties include those represented by the following formulas (a7) and (a8), and particularly preferably a structure represented by the following formula (a8).

[Formula 53]

As such a cation part, although an iodonium salt or a sulfonium salt may be sufficient, a sulfonium salt is preferable from an acid generation efficiency point.

Therefore, as an anion part of the onium salt which has a naphthalene ring in a cation part, the anion which can form a sulfonium salt is preferable.

As an anion part of such a photo-acid generator, the fluoroalkyl sulfonic acid ion or the aryl sulfonic acid ion in which part or all of the hydrogen atoms were fluorinated.

The alkyl group in the fluoroalkylsulfonic acid ion may be linear, branched or cyclic, having 1 to 20 carbon atoms, and preferably 1 to 10 carbon atoms from the bulkiness of the generated acid and its diffusion distance. In particular, the branched or annular one is preferable because the diffusion distance is short. Moreover, a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group etc. are mentioned as a preferable thing from the point which can be synthesize | combined cheaply.

The aryl group in the aryl sulfonic acid ion is an aryl group having 6 to 20 carbon atoms, and examples thereof include a phenyl group and a naphthyl group which may or may not be substituted with an alkyl group or a halogen atom. In particular, an aryl group having 6 to 10 carbon atoms is preferable from the point that can be synthesized at low cost. Preferable specific examples include phenyl group, toluenesulfonyl group, ethylphenyl group, naphthyl group, methylnaphthyl group and the like.

In the fluoroalkylsulfonic acid ions or the arylsulfonic acid ions, the fluorination rate in the case where some or all of the hydrogen atoms are fluorinated is preferably 10% or more and 100% or less, more preferably 50% or more and 100% or less. In particular, it is preferable to replace all hydrogen atoms with fluorine atoms because the strength of the acid becomes stronger. Specific examples thereof include trifluoromethanesulfonate, perfluorobutanesulfonate, perfluorooctanesulfonate, perfluorobenzenesulfonate, and the like.

Among these, what is represented by a following formula (a9) is mentioned as a preferable anion part.

[Formula 54]

In said Formula (a9), R <^20a> is group represented by following formula (a10), (a11), and (a12).

[Formula 55]

In said formula (a10), x represents the integer of 1 or more and 4 or less. In the formula (a11), R ^21a represents a hydrogen atom, a hydroxyl group, a linear or branched alkyl group having 1 to 6 carbon atoms, or a linear or branched alkoxy group having 1 to 6 carbon atoms, y Represents an integer of 1 or more and 3 or less. Among them, trifluoromethanesulfonate and perfluorobutanesulfonate are preferable from the viewpoint of safety.

Moreover, as an anion part, what contains nitrogen represented by following formula (a13) and (a14) can also be used.

[Formula 56]

In the formulas (a13) and (a14), X ^a represents a linear or branched alkylene group in which at least one hydrogen atom is substituted with a fluorine atom, and the number of carbon atoms in the alkylene group is 2 or more and 6 or less, preferably 3 or more and 5 or less, Most preferably, it is 3 carbon atoms. In addition, Y ^a and Z ^a each independently represent a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and the number of carbon atoms in the alkyl group is 1 or more and 10 or less, preferably 1 or more and 7 or less, More preferably, it is 1 or more and 3 or less.

The smaller the number of carbon atoms of the alkylene group of X ^a or the number of carbon atoms of the alkyl group of Y ^a , Z ^a , the better the solubility in the organic solvent is preferable.

In addition, in the alkylene group of X ^a or the alkyl group of Y ^a and Z ^a, the higher the number of hydrogen atoms substituted with fluorine atoms, the more preferable the acid strength becomes, which is preferable. The proportion of the fluorine atoms in the alkylene group or the alkyl group, that is, the fluorination rate, is preferably 70% or more and 100% or less, more preferably 90% or more and 100% or less, most preferably perfluorine in which all hydrogen atoms are substituted with fluorine atoms A roalkylene group or a perfluoroalkyl group.

As an onium salt which has a naphthalene ring in such a cation part, the compound represented by following formula (a15) and (a16) is mentioned.

[Formula 57]

Sixth examples of suitable photoacid generators include bis (p-toluenesulfonyl) diazomethane, bis (1,1-dimethylethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, Bissulfonyl diazomethanes such as bis (2,4-dimethylphenylsulfonyl) diazomethane; p-toluenesulfonic acid 2-nitrobenzyl, p-toluenesulfonic acid 2,6-dinitrobenzyl, nitrobenzyltosylate, dinitrobenzyltosylate, nitrobenzylsulfonato, nitrobenzyl carbonate, dinitrobenzyl carbonate Nitrobenzyl derivatives such as these; Pyrogarol trimesylate, pyrogarol tritosylate, benzyltosylate, benzylsulfonato, N-methylsulfonyloxysuccinimide, N-trichloromethylsulfonyloxysuccinimide, N-phenylsulfonyl Sulfonic acid esters such as oxymaleimide and N-methylsulfonyloxyphthalimide; Trifluoromethanesulfonic acid esters such as N-hydroxyphthalimide and N-hydroxynaphthalimide; Diphenyl iodonium hexafluorophosphate, (4-methoxyphenyl) phenyl iodonium trifluoromethanesulfonato, bis (p-tert-butylphenyl) iodonium trifluoromethanesulfonato, triphenylsulfonium Onium salts such as hexafluorophosphate, (4-methoxyphenyl) diphenylsulfonium trifluoromethanesulfonato, and (p-tert-butylphenyl) diphenylsulfonium trifluoromethanesulfonato; Benzointosylates such as benzointosylate and α-methylbenzointosylate; Other diphenyl iodonium salt, the triphenyl sulfonium salt, the phenyl diazonium salt, benzyl carbonate, etc. are mentioned.

When using in combination with a hydrogen barrier agent (B), the naphthalic acid derivative represented by a following formula (c-5) is mentioned as an especially preferable photo-acid generator.

[Formula 58]

(In formula (c-5), R ^22a is a monovalent organic group, R ^23a , R ^24a , R ^25a and R ^26a are each independently a hydrogen atom or a monovalent organic group, R ^23a , R ^24a , and R ^24a and R ^25a , or R ^25a and R ^26a may be bonded to each other to form a ring.)

The organic group as R ^22a is not particularly limited within the scope of not impairing the object of the present invention. The said organic group may be a hydrocarbon group and may contain hetero atoms, such as O, N, S, P, and a halogen atom. Moreover, the structure of the said organic group may be linear, branched, cyclic, or the combination of these structures may be sufficient as it.

As an organic group suitable as R <^22a> , the C1-C18 aliphatic hydrocarbon group which may be substituted by the halogen atom and / or the alkylthio group, the C6-C20 aryl group which may have a substituent, and a substituent An aralkyl group having 7 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, optionally having a substituent, a camphor-10-yl group, and the following formula (c-5a):

-R ^27a- (O) _a -R ^28a- (O) _b -Y ¹ -R ^29a ... (c-5a)

(In formula (c-5a), Y <^1> is a single bond or an alkanediyl group of 1 to 4 carbon atoms. R ^27a and R ^28a are each an egg having 2 to 6 carbon atoms which may be substituted with a halogen atom.) An allylene group having 6 to 20 carbon atoms which may be substituted with a candiyl group or a halogen atom, R ^29a is an alkyl group having 1 to 18 carbon atoms and an alicyclic hydrocarbon group having 3 to 12 carbon atoms, which may be substituted with a halogen atom; And an aryl group having 6 to 20 carbon atoms which may be substituted with a halogen atom, or an aralkyl group having 7 to 20 carbon atoms that may be substituted with a halogen atom, a and b are each 0 or 1, and at least one of a and b. Is 1)

The group represented by is mentioned.

When the organic group as R ^22a has a halogen atom as a substituent, the halogen atom includes chlorine atom, bromine atom, iodine atom and fluorine atom.

When the organic group as R ^22a is an alkyl group having 1 to 18 carbon atoms substituted with an alkylthio group, the alkyl atom group preferably has 1 to 18 carbon atoms.

Examples of the alkylthio group having 1 to 18 carbon atoms include methylthio group, ethylthio group, n-propylthio group, isopropylthio group, n-butylthio group, sec-butylthio group, tert-butylthio group, Isobutylthio group, n-pentylthio group, isopentylthio group, tert-pentylthio group, n-hexylthio group, n-heptylthio group, isoheptylthio group, tert-heptylthio group, n-octylthio group , Isooctylthio group, tert-octylthio group, 2-ethylhexylthio group, n-nonylthio group, n-decylthio group, n-undecylthio group, n-dodecylthio group, n-tridecylthio group, n -Tetradecylthio group, n-pentadecylthio group, n-hexadecylthio group, n-heptadecylthio group, and n-octadecylthio group are mentioned.

When the organic group as R ^{22a is} an aliphatic hydrocarbon group having 1 to 18 carbon atoms which may be substituted with a halogen atom and / or an alkylthio group, the aliphatic hydrocarbon group may contain an unsaturated double bond.

The structure of the aliphatic hydrocarbon group is not particularly limited, and may be linear, branched, cyclic, or a combination of these structures.

The allyl group and 2-methyl-2-propenyl group are mentioned as a suitable example when the organic group as R <^22a> is an alkenyl group.

Suitable examples when the organic group as R ^22a is an alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, isobutyl group, n-pentyl group, Isopentyl, tert-pentyl, n-hexyl, n-hexane-2-yl, n-hexane-3-yl, n-heptyl, n-heptan-2-yl, n-heptan-3-yl , Isoheptyl group, tert-heptyl group, n-octyl group, isooctyl group, tert-octyl group, 2-ethylhexyl group, n-nonyl group, isononyl group, n-decyl group, n-undecyl group, n- A dodecyl group, n-tridecyl group, n- tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, and n-octadecyl group are mentioned.

When the organic group as R ^22a is an alicyclic hydrocarbon group, examples of the alicyclic hydrocarbon constituting the main skeleton of the alicyclic hydrocarbon group include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclodecane, Bicyclo [2.1.1] hexane, bicyclo [2.2.1] heptane, bicyclo [3.2.1] octane, bicyclo [2.2.2] octane and adamantane. As an alicyclic hydrocarbon group, the group remove | excluding one hydrogen atom from these alicyclic hydrocarbons is preferable.

Suitable examples when the organic group as R ^{22a is} an aliphatic hydrocarbon group substituted with a halogen atom include trifluoromethyl group, pentafluoroethyl group, 2-chloroethyl group, 2-bromoethyl group, heptafluoro-n-propyl group, 3- Bromopropyl group, nonafluoro-n-butyl group, tridecafluoro-n-hexyl group, heptadecafluoro-n-octyl group, 2,2,2-trifluoroethyl group, 1,1-di Fluoroethyl group, 1,1-difluoro-n-propyl group, 1,1,2,2-tetrafluoro-n-propyl group, 3,3,3-trifluoro-n-propyl group, 2 , 2,3,3,3-pentafluoro-n-propyl group, 2-norbornyl-1,1-difluoroethyl group, 2-norbornyltetrafluoroethyl group and 3-adamantyl-1 And 1,2,2-tetrafluoropropyl groups.

Suitable examples when the organic group as R ^22a is an aliphatic hydrocarbon group substituted with an alkylthio group include 2-methylthioethyl group, 4-methylthio-n-butyl group and 2-n-butylthioethyl group.

Suitable examples when the organic group as R ^22a is an aliphatic hydrocarbon group substituted with a halogen atom and an alkylthio group include a 3-methylthio-1,1,2,2-tetrafluoro-n-propyl group.

As a suitable example in the case where the organic group as R <^22a> is an aryl group, a phenyl group, a naphthyl group, and a biphenylyl group are mentioned.

Suitable examples in the case where the organic group as R ^{22a is} an aryl group substituted with a halogen atom include a pentafluorophenyl group, a chlorophenyl group, a dichlorophenyl group and a trichlorophenyl group.

Suitable examples when the organic group as R ^22a is an aryl group substituted with an alkylthio group include 4-methylthiophenyl group, 4-n-butylthiophenyl group, 4-n-octylthiophenyl group, and 4-n-dodecylthiophenyl group. Can be.

Suitable examples when the organic group as R ^22a is an aryl group substituted with a halogen atom and an alkylthio group include 1,2,5,6-tetrafluoro-4-methylthiophenyl group, 1,2,5,6-tetrafluoro A 4-n-butylthio phenyl group and a 1,2,5,6- tetrafluoro-4-n-dodecyl thiophenyl group are mentioned.

Suitable examples in the case where the organic group as R ^22a is an aralkyl group include benzyl group, phenethyl group, 2-phenylpropan-2-yl group, diphenylmethyl group and triphenylmethyl group.

Suitable examples when the organic group as R ^{22a is} an aralkyl group substituted with a halogen atom include pentafluorophenylmethyl group, phenyldifluoromethyl group, 2-phenyltetrafluoroethyl group, and 2- (pentafluorophenyl) ethyl group. have.

As a suitable example when the organic group as R <^22a> is an aralkyl group substituted by the alkylthio group, p-methylthio benzyl group is mentioned.

Suitable examples of the case where the organic group as R ^22a is an aralkyl group substituted with a halogen atom and an alkylthio group include a 2- (2,3,5,6-tetrafluoro-4-methylthiophenyl) ethyl group.

Suitable examples when the organic group as R ^22a is an alkylaryl group include 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 3-isopropylphenyl group, 4-isopropylphenyl group, 4-n-butylphenyl group, 4- Isobutylphenyl group, 4-tert-butylphenyl group, 4-n-hexylphenyl group, 4-cyclohexylphenyl group, 4-n-octylphenyl group, 4- (2-ethyl-n-hexyl) phenyl group, 2,3-dimethylphenyl group , 2,4-dimethylphenyl group, 2,5-dimethylphenyl group, 2,6-dimethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, 2,4-di-tert-butylphenyl group, 2,5 -Di-tert-butylphenyl group, 2,6-di-tert-butylphenyl group, 2,4-di-tert-pentylphenyl group, 2,5-di-tert-pentylphenyl group, 2,5-di-tert-octyl Phenyl group, 2-cyclohexylphenyl group, 3-cyclohexylphenyl group, 4-cyclohexylphenyl group, 2,4,5-trimethylphenyl group, 2,4,6-trimethylphenyl group, 2,4,6-triisopropylphenyl group Can be.

The group represented by formula (c-5a) is an ether group containing group.

In the formula (c-5a), examples of the alkanediyl group having 1 to 4 carbon atoms represented by Y ¹ include a methylene group, an ethane-1,2-diyl group, an ethane-1,1-diyl group, and propane. -1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, butane-1,3-diyl group, butane-2,3-diyl group, butane-1,2- Diyl group is mentioned.

In the formula (c-5a), examples of the alkanediyl group having 2 to 6 carbon atoms represented by R ^27a or R ^28a include an ethane-1,2-diyl group, propane-1,3-diyl group, and propane. -1,2-diyl group, butane-1,4-diyl group, butane-1,3-diyl group, butane-2,3-diyl group, butane-1,2-diyl group, pentane-1,5- Diyl group, pentane-1,3-diyl group, pentane-1,4-diyl group, pentane-2,3-diyl group, hexane-1,6-diyl group, hexane-1,2-diyl group, hexane- 1,3-diyl group, hexane-1,4-diyl group, hexane-2,5-diyl group, hexane-2,4-diyl group, hexane-3,4-diyl group is mentioned.

In the formula (c-5a), when R ^27a or R ^28a is an alkanediyl group having 2 to 6 carbon atoms substituted with a halogen atom, the halogen atom includes a chlorine atom, bromine atom, iodine atom and fluorine atom. have. Examples of the alkanediyl group substituted with a halogen atom include tetrafluoroethane-1,2-diyl group, 1,1-difluoroethane-1,2-diyl group, 1-fluoroethane-1,2-di Diary, 1,2-difluoroethane-1,2-diyl group, hexafluoropropane-1,3-diyl group, 1,1,2,2-tetrafluoropropane-1,3-diyl group, And 1,1,2,2-tetrafluoropentane-1,5-diyl groups.

In the formula (c-5a), examples of the case where R ^27a or R ^28a is an arylene group include 1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group, 2,5-dimethyl- 1,4-phenylene group, biphenyl-4,4'-diyl group, diphenylmethane-4,4'-diyl group, 2,2-diphenylpropane-4,4'-diyl group, naphthalene-1, 2-diyl group, naphthalene-1,3-diyl group, naphthalene-1,4-diyl group, naphthalene-1,5-diyl group, naphthalene-1,6-diyl group, naphthalene-1,7-diyl group, Naphthalene-1,8-diyl group, naphthalene-2,3-diyl group, naphthalene-2,6-diyl group, naphthalene-2,7-diyl group is mentioned.

In the formula (c-5a), when R ^27a or R ^28a is an arylene group substituted with a halogen atom, the halogen atom includes a chlorine atom, bromine atom, iodine atom and fluorine atom. As an example of the arylene group substituted by the halogen atom, a 2,3,5,6- tetrafluoro-1,4-phenylene group is mentioned.

In the formula (c-5a), examples of the alkyl group having 1 to 18 carbon atoms which may have a branch represented by R ^29a include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group and sec. -Butyl group, tert-butyl group, isobutyl group, n-pentyl group, isopentyl group, tert-pentyl group, n-hexyl group, n-hexane-2-yl group, n-hexane-3-yl group, n- Heptyl group, n-heptan-2-yl group, n-heptan-3-yl group, isoheptyl group, tert-heptyl group, n-octyl group, isooctyl group, tert-octyl group, 2-ethylhexyl group, n-no Nyl group, isononyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group and n-octadecyl group.

In formula (c-5a), when R <^29a> is a C1-C18 alkyl group substituted by the halogen atom, a halogen atom includes a chlorine atom, a bromine atom, an iodine atom, and a fluorine atom. Examples of the alkyl group substituted with a halogen atom include trifluoromethyl group, pentafluoroethyl group, heptafluoro-n-propyl group, nonafluoro-n-butyl group, tridecafluoro-n-hexyl group, heptadecafluoro Rho-n-octyl group, 2,2,2-trifluoroethyl group, 1,1-difluoroethyl group, 1,1-difluoro-n-propyl group, 1,1,2,2-tetrafluoro Rho-n-propyl group, 3,3,3-trifluoro-n-propyl group, 2,2,3,3,3-pentafluoro-n-propyl group, 1,1,2,2-tetra A fluoro tetradecyl group is mentioned.

In the formula (c-5a), when R ^29a is an alicyclic hydrocarbon group having 3 to 12 carbon atoms, examples of the alicyclic hydrocarbon constituting the main skeleton of the alicyclic hydrocarbon group include cyclopropane, cyclobutane, Cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclodecane, bicyclo [2.1.1] hexane, bicyclo [2.2.1] heptane, bicyclo [3.2.1] octane, bicyclo [2.2.2] octane And adamantane. As an alicyclic hydrocarbon group, the group remove | excluding one hydrogen atom from these alicyclic hydrocarbons is preferable.

In the formula (c-5a), when R ^29a is an aryl group, a halogenated aryl group, an aralkyl group, or a halogenated aralkyl group, suitable examples of these groups are the same as those when R ^22a is a group of these.

Among the groups represented by the formula (c-5a), a suitable group is a group in which a carbon atom bonded to a sulfur atom is substituted with a fluorine atom in the group represented by R ^27a . The number of carbon atoms of such a suitable group is preferably 2 or more and 18 or less.

As R ^{22a, a} perfluoroalkyl group having 1 to 8 carbon atoms is preferable. Moreover, since it is easy to form a high definition resist pattern, camphor-10- diary is also preferable as ^R22a .

In formula (c-5), R ^23a to R ^26a are a hydrogen atom or a monovalent organic group. R ^23a and R ^24a , R ^24a and R ^25a , or R ^25a and R ^26a may be bonded to each other to form a ring. For example, an acenaphthene skeleton may be formed by combining R ^25a and R ^26a to form a five-membered ring together with a naphthalene ring.

As a monovalent organic group, C4-C18 alkoxy group which may be substituted by alicyclic hydrocarbon group, a heterocyclic group (heterocyclyl group), or a halogen atom, and may have a branch; Heterocyclyloxy group; An alkylthio group having 4 to 18 carbon atoms which may be substituted with an alicyclic hydrocarbon group, a heterocyclic group (heterocyclyl group), or a halogen atom and may have a branch; Heterocyclylthio group; It is preferable.

Moreover, the group in which the methylene group of the arbitrary position which is not adjacent to the oxygen atom of the said alkoxy group is substituted by -CO- is also preferable.

Preference is given to those in which the alkoxy group is interrupted by an -O-CO- bond or -O-CO-NH- bond. The left end of the -O-CO- bond and -O-CO-NH- bond is closer to the naphthalic acid nucleus in the alkoxy group.

In addition, an alkylthio group having 4 to 18 carbon atoms which may be substituted with an alicyclic hydrocarbon group, a heterocyclic group or a halogen atom and may have a branch is preferable as R ^23a to R ^26a .

It is also preferable that the methylene group at any position not adjacent to the sulfur atom of the alkylthio group is substituted with -CO-.

Preferred are also those wherein the alkylthio group is interrupted by an -O-CO- bond or -O-CO-NH- bond. The left end of the -O-CO- bond and -O-CO-NH- bond is closer to the naphthalic acid nucleus in the alkylthio group.

As R ^23a to R ^26a , R ^23a is an organic group, R ^24a to R ^26a is a hydrogen atom, R ^24a is an organic group, and R ^23a , R ^25a and R ^26a are preferably hydrogen atoms. Moreover, all of hydrogen atoms may be sufficient as R <^23a> -R <^26a> .

Examples of the case where R ^23a to R ^26a are an unsubstituted alkoxy group include n-butyloxy group, sec-butyloxy group, tert-butyloxy group, isobutyloxy group, n-pentyloxy group, isopentyloxy group, tert-pentyloxy group, n-hexyloxy group, n-heptyloxy group, isoheptyloxy group, tert-heptyloxy group, n-octyloxy group, isooctyloxy group, tert-octyloxy group, 2-ethylhexyl group , n-nonyloxy group, n-decyloxy group, n-undecyloxy group, n-dodecyloxy group, n-tridecyloxy group, n-tetradecyloxy group, n-pentadecyloxy group, n-hexadec A siloxy group, n-heptadecyloxy group, n-octadecyloxy group is mentioned.

Examples of the case where R ^23a to R ^26a are an unsubstituted alkylthio group include n-butylthio group, sec-butylthio group, tert-butylthio group, isobutylthio group, n-pentylthio group, and isopentylthio group. , tert-pentylthio group, n-hexylthio group, n-heptylthio group, isoheptylthio group, tert-heptylthio group, n-octylthio group, isooctylthio group, tert-octylthio group, 2-ethylhex Silthio group, n-nonylthio group, n-decylthio group, n-undecylthio group, n-dodecylthio group, n-tridecylthio group, n-tetradecylthio group, n-pentadecylthio group, n- Hexadecylthio group, n-heptadecylthio group, n-octadecylthio group is mentioned.

Examples of the alicyclic hydrocarbon constituting the main skeleton of the alicyclic hydrocarbon group when R ^23a to R ^26a are an alkoxy group or alkylthio group substituted with an alicyclic hydrocarbon group include cyclopropane, cyclobutane, cyclopentane, cyclohexane and cyclo Heptane, cyclooctane, cyclodecane, bicyclo [2.1.1] hexane, bicyclo [2.2.1] heptane, bicyclo [3.2.1] octane, bicyclo [2.2.2] octane and adamantane. have. As an alicyclic hydrocarbon group, the group remove | excluding one hydrogen atom from these alicyclic hydrocarbons is preferable.

When R ^23a to R ^26a are an alkoxy group or an alkylthio group substituted with a heterocyclic group, or R ^23a to R ^26a is a heterocyclyloxy group, examples of the heterocycle constituting the main skeleton of the heterocyclic group or heterocyclyloxy group Pyrrole, thiophene, furan, pyran, thiopyran, imidazole, pyrazole, thiazole, isothiazole, oxazole, isoxazole, pyridine, pyrazine, pyrimidine, pyridazine, pyrrolidine, pyrazoli Dean, imidazolidine, isooxazolidine, isothiazolidine, piperidine, piperazine, morpholine, thiomorpholine, chromoman, thiochromoman, isochromoman, isothiochromoman, indolin, Isoindolin, pyrindine, indolizin, indole, indazole, purine, quinolysin, isoquinoline, quinoline, naphthyridine, phthalazine, quinoxaline, quinazoline, cinnoline, pteridine, acridine , Perimidine, phenanthroline, carbazole, carboline, phenazine, antiridine, thiadiazole, oxadiazole, Liao Jin, there may be mentioned triazole, tetrazole, benzimidazole, benzoxazole, benzothiazole, benzo thiadiazole, benzo Fu Roxanne, naphthyl toy imidazole, benzotriazole, tetra-aza indene. Moreover, the saturated heterocycle which hydrogenated to the ring which has a conjugated bond among these heterocycles is also preferable.

As a heterocyclic group contained in the heterocyclic group or heterocyclyloxy group which substituted the alkoxy group or the alkylthio group, group which removed one hydrogen atom from the said heterocycle is preferable.

Examples of the case where R ^23a to R ^26a are an alkoxy group containing an alicyclic hydrocarbon group include cyclopentyloxy group, methylcyclopentyloxy group, cyclohexyloxy group, fluorocyclohexyloxy group, chlorocyclohexyloxy group and cyclohexyl Methyloxy group, methylcyclohexyloxy group, norbornyloxy group, ethylcyclohexyloxy group, cyclohexylethyloxy group, dimethylcyclohexyloxy group, methylcyclohexylmethyloxy group, norbornylmethyloxy group, trimethylcyclohex Siloxy group, 1-cyclohexylbutyloxy group, adamantyloxy group, menthyloxy group, n-butylcyclohexyloxy group, tert-butylcyclohexyloxy group, bornyloxy group, isobornyloxy group, decahydronaphthyloxy group , Dicyclopentadieneoxy group, 1-cyclohexylpentyloxy group, methyl adamantyloxy group, adamantylmethyloxy group, 4-pentylcyclohexyloxy group, cyclohexylcyclohexyloxy group, adamantylethyl jade Group, may be mentioned dimethyl an adamantyloxy.

Examples of the case where R ^23a to R ^26a are a heterocyclyloxy group include tetrahydrofuranyloxy group, perfuryloxy group, tetrahydroperfuryloxy group, tetrahydropyranyloxy group, butyrolactoneyloxy group and indolyloxy group. have.

Examples of the case where R ^23a to R ^26a are alkylthio groups containing an alicyclic hydrocarbon group include cyclopentylthio group, cyclohexylthio group, cyclohexylmethylthio group, norbornylthio group, and isononorbornylthio group. .

Examples of the case where R ^23a to R ^26a are heterocyclylthio group include perfurylthio group and tetrahydrofuranylthio group.

Examples of the case where R ^23a to R ^26a are a group in which a methylene group at any position not adjacent to the oxygen atom of the alkoxy group are substituted with -CO- are 2-ketobutyl-1-oxy group and 2-ketopentyl-1- Oxy group, 2-ketohexyl-1-oxy group, 2-ketoheptyl-1-oxy group, 2-ketooctyl-1-oxy group, 3-ketobutyl-1-oxy group, 4-ketopentyl-1 -Oxy group, 5-ketohexyl-1-oxy group, 6-ketoheptyl-1-oxy group, 7-ketooctyl-1-oxy group, 3-methyl-2-ketopentane-4-oxy group, 2 -Ketopentane-4-oxy group, 2-methyl-2-ketopentane-4-oxy group, 3-ketoheptan-5-oxy group, and 2-adamantanone 5-oxy group are mentioned.

Examples of the case where R ^23a to R ^26a are a group in which a methylene group at any position not adjacent to the sulfur atom of the alkylthio group are substituted with -CO- are 2-ketobutyl-1-thio group and 2-ketopentyl-1. -Thio group, 2-ketohexyl-1-thio group, 2-ketoheptyl-1-thio group, 2-ketooctyl-1-thio group, 3-ketobutyl-1-thio group, 4-ketopentyl- 1-thio group, 5-ketohexyl-1-thio group, 6-ketoheptyl-1-thio group, 7-ketooctyl-1-thio group, 3-methyl-2-ketopentane-4-thio group, 2-ketopentane-4-thio group, 2-methyl-2- ketopentane-4-thio group, and 3-ketoheptan-5-thio group are mentioned.

As a suitable example of the naphthalic acid derivative represented by a formula (c-5), the following compounds are mentioned.

[Formula 59]

[Formula 60]

[Formula 61]

[Formula 62]

[Formula 63]

[Formula 64]

[Formula 65]

[Formula 66]

[Formula 67]

In addition, as other photo-acid generators, bis (p-toluenesulfonyl) diazomethane, methylsulfonyl-p-toluenesulfonyldiazomethane, 1-cyclohexylsulfonyl-1- (1,1-dimethylethyl Sulfonyl) diazomethane, bis (1,1-dimethylethylsulfonyl) diazomethane, bis (1-methylethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (2, 4-dimethylphenylsulfonyl) diazomethane, bis (4-ethylphenylsulfonyl) diazomethane, bis (3-methylphenylsulfonyl) diazomethane, bis (4-methoxyphenylsulfonyl) diazomethane, Bissulfonyldiazomethanes such as bis (4-fluorophenylsulfonyl) diazomethane, bis (4-chlorophenylsulfonyl) diazomethane and bis (4-tert-butylphenylsulfonyl) diazomethane ; 2-methyl-2- (p-toluenesulfonyl) propiophenone, 2- (cyclohexylcarbonyl) -2- (p-toluenesulfonyl) propane, 2-methanesulfonyl-2-methyl- (p- Sulfonylcarbonylalkanes such as methylthio) propiophenone and 2,4-dimethyl-2- (p-toluenesulfonyl) pentan-3-one; 1-p-toluenesulfonyl-1-cyclohexylcarbonyldiazomethane, 1-diazo-1-methylsulfonyl-4-phenyl-2-butanone, 1-cyclohexylsulfonyl-1-cyclohexylcar Bonyldiazomethane, 1-diazo-1-cyclohexylsulfonyl-3,3-dimethyl-2-butanone, 1-diazo-1- (1,1-dimethylethylsulfonyl) -3,3- Dimethyl-2-butanone, 1-acetyl-1- (1-methylethylsulfonyl) diazomethane, 1-diazo-1- (p-toluenesulfonyl) -3,3-dimethyl-2-butanone , 1-diazo-1-benzenesulfonyl-3,3-dimethyl-2-butanone, 1-diazo-1- (p-toluenesulfonyl) -3-methyl-2-butanone, 2-dia Crude-2- (p-toluenesulfonyl) cyclohexyl, 2-diazo-2-benzenesulfonylacetic acid-tert-butyl, 2-diazo-2-methanesulfonylacetic acid isopropyl, 2-diazo- Sulfonylcarbonyldiazomethanes such as 2-benzenesulfonyl acetate cyclohexyl and 2-diazo-2- (p-toluenesulfonyl) acetic acid-tert-butyl; nitrobenzyl derivatives such as p-toluenesulfonic acid-2-nitrobenzyl, p-toluenesulfonic acid-2,6-dinitrobenzyl and p-trifluoromethylbenzenesulfonic acid-2,4-dinitrobenzyl; Methanesulfonic acid ester of pyrogarol, benzenesulfonic acid ester of pyrogarol, p-toluenesulfonic acid ester of pyrogarol, p-methoxybenzenesulfonic acid ester of pyrogarol, mesitylene sulfonic acid ester of pyrogarol, pyrogarol P-methoxybenzenesulfonic acid of benzylsulfonic acid ester of alkyl, methanesulfonic acid ester of alkyl gallate, benzenesulfonic acid ester of alkyl gallate, p-toluenesulfonic acid ester of alkyl gallate, p-methoxybenzenesulfonic acid of alkyl gallate Esters of polyhydroxy compounds such as esters, mesitylene sulfonic acid esters of alkyl gallate and benzyl sulfonic acid esters of alkyl gallates, and aliphatic or aromatic sulfonic acids; Etc. can be mentioned.

These photo-acid generators can be used individually or in combination of 2 or more types.

These photoacid generators may be used alone, or may be used in combination of two or more thereof. Moreover, it is preferable to make content of a photo-acid generator into 0.1 mass% or more and 10 mass% or less with respect to the total mass of the photosensitive composition of a 2nd aspect, and it is more preferable to set it as 0.5 mass% or more and 3 mass% or less. By making the usage-amount of a photo-acid generator into the said range, it is easy to prepare the photosensitive composition of the 2nd aspect which has favorable sensitivity and is excellent in storage stability as a uniform solution.

It does not specifically limit as resin in which the solubility with respect to an alkali increases by the action of an acid, Any resin which increases the solubility with respect to an alkali by the action of an acid can be used. Especially, it is preferable to contain at least 1 sort (s) of resin chosen from the group which consists of novolak resin (B1), polyhydroxy styrene resin (B2), and acrylic resin (B3).

[Novolak Resin (B1)]

As novolak resin (B1), resin containing the structural unit represented by a following formula (b1) can be used.

[Formula 68]

In said formula (b1), R <^1b> represents an acid dissociable, dissolution inhibiting group, R <^2b> , R <^3b> respectively independently represents a hydrogen atom or a C1 or more alkyl group.

Examples of the acid dissociable, dissolution inhibiting group represented by R ^1b include groups represented by the following formulas (b2) and (b3), linear, branched, or cyclic alkyl groups having 1 to 6 carbon atoms, and vinyloxyethyl groups. It is preferable that it is a tetrahydropyranyl group, a tetrafuranyl group, or a trialkyl silyl group.

[Formula 69]

In said formula (b2), (b3), R <^4b> , R <^5b> respectively independently represents a hydrogen atom or a C1-C6 linear or branched alkyl group, R <^6b> C1-C10 is 10 or less Represents a linear, branched or cyclic alkyl group, R ^7b represents a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, and o represents 0 or 1.

Examples of the linear or branched alkyl group include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group and neopentyl group. Moreover, a cyclopentyl group, a cyclohexyl group, etc. are mentioned as said cyclic alkyl group.

Here, as the acid dissociable, dissolution inhibiting group represented by the formula (b2), specifically, a methoxyethyl group, ethoxyethyl group, n-propoxyethyl group, isopropoxyethyl group, n-butoxyethyl group, isobutoxyethyl group, tert-butoxyethyl group, cyclohexyloxyethyl group, methoxypropyl group, ethoxypropyl group, 1-methoxy-1-methyl-ethyl group, 1-ethoxy-1-methylethyl group, etc. are mentioned. Specific examples of the acid dissociable, dissolution inhibiting group represented by the formula (b3) include tert-butoxycarbonyl group, tert-butoxycarbonylmethyl group, and the like. Examples of the trialkylsilyl group include those having 1 to 6 carbon atoms in each alkyl group such as trimethylsilyl group and tri-tert-butyldimethylsilyl group.

[Polyhydroxystyrene Resin (B2)]

As polyhydroxy styrene resin (B2), resin containing the structural unit represented by a following formula (b4) can be used.

[Formula 70]

In said formula (b4), R <^8b> represents a hydrogen atom or a C1- ^C6 alkyl group, and R <^9b> represents an acid dissociable, dissolution inhibiting group.

The alkyl group having 1 to 6 carbon atoms is, for example, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms. Examples of the linear or branched alkyl group include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group and neopentyl group. Cyclopentyl group, cyclohexyl group, etc. are mentioned as cyclic alkyl group.

As the acid dissociable, dissolution inhibiting group represented by R ^9b , the same acid dissociable, dissolution inhibiting groups as exemplified in the formulas (b2) and (b3) can be used.

Moreover, polyhydroxy styrene resin (B2) can contain another polymeric compound as a structural unit in order to control physical and chemical characteristics suitably. As such a polymeric compound, a well-known radically polymerizable compound and an anionic polymerizable compound are mentioned. Moreover, as such a polymeric compound, Monocarboxylic acids, such as acrylic acid, methacrylic acid, a crotonic acid; Dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid; It has carboxyl group and ester bond, such as 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl maleic acid, 2-methacryloyloxyethyl phthalic acid, 2-methacryloyloxyethyl hexahydrophthalic acid, etc. Methacrylic acid derivatives; (Meth) acrylic-acid alkylesters, such as methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylate; (Meth) acrylic-acid hydroxyalkyl esters, such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; (Meth) acrylic acid aryl esters, such as phenyl (meth) acrylate and benzyl (meth) acrylate; Dicarboxylic acid diesters such as diethyl maleate and dibutyl fumarate; Vinyl group-containing aromatic compounds such as styrene, α-methylstyrene, chlorostyrene, chloromethylstyrene, vinyltoluene, hydroxystyrene, α-methylhydroxystyrene, and α-ethylhydroxystyrene; Vinyl group-containing aliphatic compounds such as vinyl acetate; Conjugated diolefins such as butadiene and isoprene; Nitrile group-containing polymerizable compounds such as acrylonitrile and methacrylonitrile; Chlorine-containing polymerizable compounds such as vinyl chloride and vinylidene chloride; Amide bond-containing polymerizable compounds such as acrylamide and methacrylamide; Etc. can be mentioned.

[Acrylic Resin (B3)]

As acrylic resin (B3), resin containing the structural unit represented by following formula (b5)-(b7) can be used.

[Formula 71]

In said formula (b5)-(b7), R <^10b> and R <^14b> -R <^19b> are respectively independently a hydrogen atom, a C1-C6 linear or branched alkyl group, a fluorine atom, or C1-C6. The following linear or branched fluorinated alkyl groups are represented, and R ^11b to R ^13b each independently represent a linear or branched alkyl group having 1 to 6 carbon atoms, and a linear or branched fluorinated compound having 1 to 6 carbon atoms. An alkyl group or an aliphatic cyclic group having 5 to 20 carbon atoms, R ^12b and R ^13b may be bonded to each other to form a hydrocarbon ring having 5 to 20 carbon atoms, together with the carbon atom to which both are bonded. , Y ^b represents an aliphatic cyclic group or alkyl group which may have a substituent, p represents an integer of 0 or more and 4 or less, and q represents 0 or 1.

Examples of the linear or branched alkyl group include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group and neopentyl group. Can be. In addition, a fluorinated alkyl group is group in which one part or all part of the hydrogen atom of the said alkyl group was substituted by the fluorine atom.

Specific examples of the aliphatic cyclic group include groups in which one or more hydrogen atoms are removed from polycycloalkanes such as monocycloalkane, bicycloalkane, tricycloalkane, and tetracycloalkane. Specifically, one is selected from monocycloalkanes such as cyclopentane, cyclohexane, cycloheptane and cyclooctane, and polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane and tetracyclododecane. The group except a hydrogen atom is mentioned. In particular, group (you may further have a substituent) remove | excluding one hydrogen atom from cyclohexane and adamantane is preferable.

When R ^12b and R ^13b are not bonded to each other to form a hydrocarbon ring, as R ^11b , R ^12b and R ^13b , since they have high contrast, resolution, depth of focus, and the like, the number of carbon atoms is 2 or more 4 It is preferable that they are the following linear or branched alkyl groups. As said R <^15b> , R <^16b> , R <^18b> , and R <^19b> , it is preferable that they are a hydrogen atom or a methyl group.

R ^12b and R ^13b may form an aliphatic cyclic group having 5 to 20 carbon atoms with the carbon atoms to which both are bonded. Specific examples of such aliphatic cyclic groups include groups in which one or more hydrogen atoms are removed from polycycloalkanes such as monocycloalkane, bicycloalkane, tricycloalkane, and tetracycloalkane. Specifically, it is one from monocycloalkane, such as cyclopentane, cyclohexane, cycloheptane, cyclooctane, and polycycloalkane, such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane. The group except the above hydrogen atom is mentioned. In particular, group (you may further have a substituent) remove | excluding one or more hydrogen atoms from cyclohexane and adamantane is preferable.

When the aliphatic cyclic group formed by R ^12b and R ^13b has a substituent on the ring skeleton, examples of the substituent include a polar group such as a hydroxyl group, a carboxy group, a cyano group, an oxygen atom (= O), and a carbon atom. 1 or more and 4 or less linear or branched alkyl groups are mentioned. Especially as a polar group, an oxygen atom (= O) is preferable.

Y <^b> is an aliphatic cyclic group or an alkyl group, The group remove | excluding one or more hydrogen atoms from polycyclo alkanes, such as a monocyclo alkan, a bicyclo alkan, a tricyclo alkan, and a tetracyclo alkan, etc. are mentioned. Specifically, it is one from monocycloalkane, such as cyclopentane, cyclohexane, cycloheptane, cyclooctane, and polycycloalkane, such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane. The group except the above hydrogen atom is mentioned. In particular, group (you may further have a substituent) remove | excluding one or more hydrogen atoms from adamantane is preferable.

When the aliphatic cyclic group of Y ^b has a substituent on the ring skeleton, examples of the substituent include a polar group such as a hydroxyl group, a carboxy group, a cyano group, an oxygen atom (= O), and one to four carbon atoms. The linear or branched alkyl group of is mentioned. Especially as a polar group, an oxygen atom (= O) is preferable.

Moreover, when Y <^b> is an alkyl group, it is preferable that they are a C1-C20 or less linear or branched alkyl group of preferably 6 or more and 15 or less. It is preferable that such an alkyl group is an alkoxyalkyl group especially, As such an alkoxyalkyl group, 1-methoxyethyl group, 1-ethoxyethyl group, 1-n-propoxyethyl group, 1-isopropoxyethyl group, 1-n-butoxy Ethyl group, 1-isobutoxyethyl group, 1-tert-butoxyethyl group, 1-methoxypropyl group, 1-ethoxypropyl group, 1-methoxy-1-methyl-ethyl group, 1-ethoxy-1-methylethyl group Etc. can be mentioned.

As a preferable specific example of the structural unit represented by said formula (b5), the structural unit represented by following formula (b5-1) (b5-33) is mentioned.

[Formula 72]

R <^20b> represents a hydrogen atom or a methyl group in said formula (b5-1) (b5-33).

As a preferable specific example of the structural unit represented by said formula (b6), the structural unit represented by following formula (b6-1) (b6-25)-is mentioned.

[Formula 73]

R <^20b> represents a hydrogen atom or a methyl group in said formula (b6-1) (b6-25).

As a preferable specific example of the structural unit represented by said formula (b7), the structural unit represented by following formula (b7-1) (b7-15) is mentioned.

[Formula 74]

R <^20b> represents a hydrogen atom or a methyl group in said formula (b7-1) (b7-15).

In addition, in the structural unit represented by said formula (b5)-(b7), acrylic resin (B3) is resin which consists of a copolymer containing the structural unit further derived from the polymeric compound which has an ether bond. desirable.

As said polymeric compound which has an ether bond, radically polymerizable compounds, such as a (meth) acrylic acid derivative which has an ether bond and an ester bond, can be illustrated, As a specific example, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, methoxytriethylene glycol (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethyl carbitol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylic The rate, methoxy polyethylene glycol (meth) acrylate, methoxy polypropylene glycol (meth) acrylate, tetrahydro perfuryl (meth) acrylate, etc. are mentioned. The polymerizable compound having an ether bond is preferably 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, and methoxytriethylene glycol (meth) acrylate. These polymerizable compounds may be used independently or may be used in combination of 2 or more type.

In addition, the acrylic resin (B3) can contain another polymeric compound as a structural unit in order to control physical and chemical characteristics suitably. As such a polymeric compound, a well-known radically polymerizable compound and an anionic polymerizable compound are mentioned.

As such a polymeric compound, For example, Monocarboxylic acids, such as acrylic acid, methacrylic acid, and crotonic acid; Dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid; It has carboxyl group and ester bond, such as 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl maleic acid, 2-methacryloyloxyethyl phthalic acid, 2-methacryloyloxyethyl hexahydrophthalic acid, etc. Methacrylic acid derivatives; (Meth) acrylic-acid alkylesters, such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and cyclohexyl (meth) acrylate; (Meth) acrylic acid hydroxyalkyl esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; (Meth) acrylic acid aryl esters, such as phenyl (meth) acrylate and benzyl (meth) acrylate; Dicarboxylic acid diesters such as diethyl maleate and dibutyl fumarate; Vinyl group-containing aromatic compounds such as styrene, α-methylstyrene, chlorostyrene, chloromethylstyrene, vinyltoluene, hydroxystyrene, α-methylhydroxystyrene, and α-ethylhydroxystyrene; Vinyl group-containing aliphatic compounds such as vinyl acetate; Conjugated diolefins such as butadiene and isoprene; Nitrile group-containing polymerizable compounds such as acrylonitrile and methacrylonitrile; Chlorine-containing polymerizable compounds such as vinyl chloride and vinylidene chloride; Amide bond-containing polymerizable compounds such as acrylamide and methacrylamide; Etc. can be mentioned.

Moreover, (meth) acrylic acid ester which has an acid non-aliphatic polycyclic group, vinyl group containing aromatic compound, etc. are mentioned as a polymeric compound. As the acid non-aliphatic aliphatic polycyclic group, tricyclodecanyl group, adamantyl group, tetracyclododecanyl group, isobornyl group, norbornyl group and the like are particularly preferable from the viewpoint of being easily obtained industrially. These aliphatic polycyclic groups may have a linear or branched alkyl group having 1 to 5 carbon atoms as a substituent.

Specifically as (meth) acrylic acid ester which has an acid non-dissociable aliphatic polycyclic group, (meth) acrylic acid ester which gives the structural unit of following formula (b8-1)-(b8-5) can be illustrated. Can be.

[Formula 75]

R <^21b> represents a hydrogen atom or a methyl group in said formula (b8-1) (b8-5).

It is preferable to use acrylic resin (B3) among said photosensitive resin. Among these acrylic resins (B3), from structural units represented by formula (b5), structural units derived from (meth) acrylic acid, structural units derived from (meth) acrylic acid alkyl esters, and (meth) acrylic acid aryl esters. Preference is given to copolymers having derived structural units.

As such a copolymer, it is preferable that it is a copolymer represented by following formula (b9).

[Formula 76]

In said formula (b9), R <^22b> represents a hydrogen atom or a methyl group, R <^23b> represents a linear or branched alkyl group of 2 or more carbon atoms, X ^b is carbon formed with the carbon atom to which it is bonded A hydrocarbon ring having 5 to 20 atoms, R ^24b represents a linear or branched alkyl group having 1 to 6 carbon atoms or an alkoxyalkyl group having 1 to 6 carbon atoms, and R ^25b represents 6 carbon atoms. The aryl group of 12 or more is shown.

In the copolymer represented by the formula (b9), s, t, u, and ｖ each represent a molar ratio of each structural unit, s is 8 mol% or more and 45 mol% or less, and t is 10 mol% or more. 65 mol% or less, u is 3 mol% or more and 25 mol% or less, and X is 6 mol% or more and 25 mol% or less.

The polystyrene reduced mass average molecular weight of the photosensitive resin becomes like this. Preferably it is 10,000 or more and 600,000 or less, More preferably, it is 20,000 or more and 400,000 or less, More preferably, it is 30,000 or more and 300,000 or less. By setting it as such a mass average molecular weight, sufficient intensity | strength of the photosensitive resin layer can be maintained without peeling property with the surface of a board | substrate, and also swelling and crack generation of the profile at the time of plating can be prevented.

Moreover, it is preferable that the photosensitive resin is resin whose dispersion degree is 1.05 or more. Here, dispersion degree is the value which divided | diluted the mass mean molecular weight by the number average molecular weight. By such a dispersion degree, the problem that the stress tolerance to desired plating and the metal layer obtained by a plating process become easy to swell can be avoided.

It is preferable to make content of resin into 5 mass% or more and 60 mass% or less with respect to the total mass of the photosensitive composition of a 2nd aspect.

It is preferable that the photosensitive composition of a 2nd aspect contains alkali-soluble resin further in order to improve crack resistance.

It is preferable that it is at least 1 sort (s) of resin chosen from the group which consists of novolak resin (C1), polyhydroxy styrene resin (C2), and acrylic resin (C3) as alkali-soluble resin.

[Novolak Resin (C1)]

The novolak resin is obtained by addition condensation of, for example, an aromatic compound having a phenolic hydroxyl group (hereinafter, simply referred to as "phenols") and an aldehyde under an acid catalyst.

Examples of the phenols include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol and p- Butylphenol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol , 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, p-phenylphenol, resorcinol, hydroquinone, hydroquinone monomethyl ether, pyrogarol, fluoroglycinol, hydroxydiphenyl, Bisphenol A, gallic acid, gallic acid ester, α-naphthol, β-naphthol and the like.

Examples of the aldehydes include formaldehyde, perfural, benzaldehyde, nitrobenzaldehyde, acetoaldehyde and the like.

Although the catalyst at the time of addition condensation reaction is not specifically limited, For example, hydrochloric acid, nitric acid, sulfuric acid, formic acid, oxalic acid, acetic acid etc. are used for an acid catalyst.

In addition, it is possible to further improve the flexibility of the novolak resin by using o-cresol, substituting a hydrogen atom of a hydroxyl group in the resin with another substituent, or by using bulky aldehydes.

Although the mass mean molecular weight of novolak resin (C1) is not specifically limited in the range which does not impair the objective of this invention, It is preferable that they are 1,000 or more and 50,000 or less.

[Polyhydroxystyrene Resin (C2)]

As a hydroxy styrene type compound which comprises polyhydroxy styrene resin (C2), p-hydroxy styrene, (alpha)-methylhydroxy styrene, (alpha)-ethyl hydroxy styrene, etc. are mentioned.

Moreover, it is preferable to set polyhydroxy styrene resin (C2) as a copolymer with a styrene resin. Examples of the styrene compounds constituting such styrene resins include styrene, chlorostyrene, chloromethylstyrene, vinyltoluene, and α-methylstyrene.

Although the mass mean molecular weight of polyhydroxy styrene resin (C2) is not specifically limited in the range which does not impair the objective of this invention, It is preferable that they are 1,000 or more and 50,000 or less.

[Acrylic Resin (C3)]

As acrylic resin (C3), it is preferable to include the structural unit derived from the polymeric compound which has an ether bond, and the structural unit derived from the polymeric compound which has a carboxy group.

As a polymeric compound which has the said ether bond, 2-methoxyethyl (meth) acrylate, methoxy triethylene glycol (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethyl carbitol (meth) Examples of (meth) acrylic acid derivatives having ether bonds and ester bonds such as acrylate, phenoxy polyethylene glycol (meth) acrylate, methoxy polypropylene glycol (meth) acrylate, and tetrahydrofurfuryl (meth) acrylate can do. The polymerizable compound having an ether bond is preferably 2-methoxyethyl acrylate or methoxy triethylene glycol acrylate. These polymerizable compounds may be used independently or may be used in combination of 2 or more type.

As a polymeric compound which has the said carboxyl group, Monocarboxylic acids, such as acrylic acid, methacrylic acid, a crotonic acid; Dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid; It has carboxyl group and ester bond, such as 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl maleic acid, 2-methacryloyloxyethyl phthalic acid, 2-methacryloyloxyethyl hexahydrophthalic acid, etc. compound; Etc. can be illustrated. The polymerizable compound having the carboxyl group is preferably acrylic acid or methacrylic acid. These polymerizable compounds may be used independently or may be used in combination of 2 or more type.

Although the mass mean molecular weight of acrylic resin (C3) is not specifically limited in the range which does not impair the objective of this invention, It is preferable that they are 50,000 or more and 800,000 or less.

When content of alkali-soluble resin makes the total of the said photosensitive resin and alkali-soluble resin 100 mass parts, 0 mass parts or more and 80 mass parts or less are preferable, and 0 mass parts or more and 60 mass parts or less are more preferable. By making content of alkali-soluble resin into the said range, there exists a tendency which can improve crack tolerance and can prevent the film | membrane at the time of image development.

It is preferable that the photosensitive composition of a 2nd aspect contains an acid diffusion control agent further for the improvement of the inch stability etc. of the film | membrane which consists of a photosensitive composition. As an acid diffusion control agent, a nitrogen-containing compound (D1) is preferable, and if necessary, organic carboxylic acid or iodine acid or its derivative (D2) of phosphorus can be contained.

[Nitrogen-containing compound (D1)]

Examples of the nitrogen-containing compound (D1) include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, tri-n-pentylamine, tribenzylamine, diethanolamine, and triethanolamine , n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, ethylenediamine, N, N, N ', N'-tetramethylethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4 '-Diaminodiphenylmethane, 4,4'-diaminodiphenylether, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenylamine, formamide, N-methylformamide, N , N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, benzamide, pyrrolidone, N-methylpyrrolidone, methylurea, 1,1-dimethylurea , 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea, imidazole, benzimidazole, 4-methylimidazole, 8-oxyquinoline, acridine , Furin, pyrrole Dean, piperidine, 2,4,6-tri (2-pyridyl) -S-triazine, morpholine, 4-methylmorpholine, piperazine, 1,4-dimethylpiperazine, 1,4-dia Xabicyclo [2.2.2] octane, a pyridine, etc. are mentioned. These may be used independently and may be used in combination of 2 or more type.

Nitrogen-containing compound (D1) is normally used in the range of 0 mass part or more and 5 mass parts or less with respect to 100 mass parts of total mass of the said photosensitive resin and alkali-soluble resin, and is used in the range which is 0 mass part or more and 3 mass parts or less. It is especially preferable.

[Organic Carboxylic Acid, or Iodine Acid or Derivatives of Phosphorus (D2)]

Among the organic carboxylic acids or the iodic acid of phosphorus or its derivative (D2), as the organic carboxylic acid, malonic acid, citric acid, malic acid, succinic acid, benzoic acid, salicylic acid and the like are particularly suitable, and salicylic acid is particularly preferable.

Examples of phosphorus iodic acid or derivatives thereof include phosphoric acid such as phosphoric acid, di-n-butyl phosphate and diphenyl ester phosphate, and derivatives such as esters thereof; Derivatives such as phosphonic acids and esters thereof such as phosphonic acid, phosphonic acid dimethyl ester, phosphonic acid di-n-butyl ester, phenylphosphonic acid, phosphonic acid diphenyl ester and phosphonic acid dibenzyl ester; Derivatives such as phosphinic acid and esters thereof such as phosphinic acid and phenylphosphinic acid; Etc. can be mentioned. Among these, phosphonic acid is especially preferable. These may be used independently and may be used in combination of 2 or more type.

Organic carboxylic acid or iodine acid or its derivative (D2) of phosphorus is normally used in the range of 0 mass part or more and 5 mass parts or less with respect to 100 mass parts of total masses of the said photosensitive resin and the said alkali-soluble resin, and 0 mass parts It is especially preferable to be used in the range of 3 mass parts or more above.

Moreover, in order to form and stabilize a salt, it is preferable to use organic carboxylic acid or iodine acid of phosphorus, or its derivative (D2) and an equivalent amount with the said nitrogen-containing compound (D1).

The photosensitive composition of a 2nd aspect contains the organic solvent. The kind of organic solvent is not specifically limited in the range which does not impair the objective of this invention, It can select from the organic solvent conventionally used for the positive photosensitive composition, and can use it suitably.

As a specific example of the organic solvent, In addition to the solvent illustrated by the photosensitive composition of a 1st aspect, ketones, such as acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, 2-heptanone; Ethylene glycol, ethylene glycol monoacetate, diethylene glycol, diethylene glycol monoacetate, propylene glycol, propylene glycol monoacetate, dipropylene glycol, monopropylene ether of dipropylene glycol monoacetate, monoethyl ether, monopropyl ether, monobutyl Polyhydric alcohols such as ether and monophenyl ether and derivatives thereof; Cyclic ethers such as dioxane; Ethyl formate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl pyruvate, ethyl ethoxyacetate, methyl methoxypropionate, ethyl ethoxypropionate, 2-hydrate Methyl hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl Esters such as acetates; Aromatic hydrocarbons such as toluene and xylene; Etc. can be mentioned. These may be used independently, or may mix and use 2 or more types.

Although content of an organic solvent is not specifically limited in the range which does not impair the objective of this invention, For example, what is necessary is just to adjust suitably in the range which becomes 2 mass% or more and 55 mass% or less of solid content concentration of the photosensitive composition. When using the photosensitive composition for the thick film use whose film thickness of the photosensitive resin layer obtained by a spin coat method etc. becomes 10 micrometers or more, the organic solvent is used in the range from which solid content concentration of a photosensitive composition will be 30 mass% or more and 55 mass% or less. It is preferable to use.

The photosensitive composition of a 2nd aspect may contain polyvinyl resin further in order to improve reversibility. As a specific example of polyvinyl resin, polyvinyl chloride, polystyrene, polyhydroxy styrene, polyvinyl acetate, polyvinyl benzoic acid, polyvinyl methyl ether, polyvinyl ethyl ether, polyvinyl alcohol, polyvinylpyrrolidone, polyvinyl Phenols and these copolymers; and the like. The polyvinyl resin is preferably polyvinyl methyl ether from a low glass transition point.

Moreover, in order to improve the adhesiveness of the hydrogen barrier film | membrane formed using the photosensitive composition and a board | substrate, especially a metal substrate, the photosensitive composition of a 2nd aspect may further contain the adhesion | attachment adjuvant.

The second photosensitive composition may further contain an acid, an acid anhydride or a high boiling point solvent in order to perform fine adjustment of the solubility in the developer.

Specific examples of the acid and acid anhydride include monocarboxylic acids such as acetic acid, propionic acid, n-butyric acid, isobutyric acid, n-valeric acid, isovaleric acid, benzoic acid and cinnamic acid; Lactic acid, 2-hydroxybutyric acid, 3-hydroxybutyric acid, salicylic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, 2-hydroxycinnamic acid, 3-hydroxycinnamic acid, 4-hydroxycinnamic acid, 5 Hydroxy monocarboxylic acids such as hydroxyisophthalic acid and silingic acid; Oxalic acid, succinic acid, glutaric acid, adipic acid, maleic acid, itaconic acid, hexahydrophthalic acid, phthalic acid, isophthalic acid, terephthalic acid, 1,2-cyclohexanedicarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, butanetetra Polyhydric carboxylic acids such as carboxylic acid, trimellitic acid, pyromellitic acid, cyclopentanetetracarboxylic acid, butanetetracarboxylic acid, 1,2,5,8-naphthalenetetracarboxylic acid; Itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, tricarbanylic acid anhydride, maleic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hymic acid anhydride, 1,2,3,4- Acid anhydrides such as butanetetracarboxylic anhydride, cyclopentanetetracarboxylic dianhydride, phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenonetetracarboxylic anhydride, ethylene glycol bis trimellitate, and glycerin tris anhydride; Etc. can be mentioned.

Moreover, as a specific example of a high boiling point solvent, N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrroli Don, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate And diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, and phenyl cellosolve acetate.

The photosensitive composition of a 2nd aspect may further contain a sensitizer in order to improve a sensitivity.

As for content of a hydrogen barrier agent (B), 0.01 mass% or more and 30 mass% or less are preferable with respect to the mass of resin corresponding to the base material component (A) in the photosensitive composition of a 2nd aspect, 0.05 mass% or more and 20 mass% % Or less is more preferable, and 0.1 mass% or more and 10 mass% or less are especially preferable. By setting it as said range, the pattern which has hydrogen barrier performance can be obtained, obtaining favorable developability.

(3) The photosensitive composition of the third aspect

The photosensitive composition of a 3rd aspect is a negative photosensitive composition containing alkali-soluble resin which has a phenolic hydroxyl group, an acid crosslinkable substance, a photoacid generator, a hydrogen barrier agent (B), and an organic solvent.

As alkali-soluble resin which has a phenolic hydroxyl group in the photosensitive composition of 3rd aspect, polyhydroxy styrene resin can be used, for example.

The polyhydroxy styrene resin has at least a structural unit derived from hydroxy styrene.

Herein, "hydroxy styrene" means a hydroxy styrene and a hydroxy styrene derivative in which a hydrogen atom bonded to the α-position of hydroxy styrene is substituted with another substituent such as a halogen atom, an alkyl group, a halogenated alkyl group, and derivatives thereof (monomer) It is assumed that the concept includes).

In the "hydroxystyrene derivative", at least the benzene ring and the hydroxyl group which couple | bond with this are hold | maintained, For example, the hydrogen atom couple | bonded with the (alpha) -position of hydroxy styrene, a halogen atom, the C1-C5 alkyl group Or an alkyl group having 1 to 5 carbon atoms bonded to the benzene ring substituted with other substituents such as a halogenated alkyl group and the hydroxyl group of hydroxystyrene, or one further to the benzene ring to which the hydroxyl group is bonded. Two or less hydroxyl groups couple | bonded (at this time, the sum total of the number of hydroxyl groups shall be 2 or more and 3 or less), etc. shall be included.

As a halogen atom, a chlorine atom, a fluorine atom, a bromine atom, etc. are mentioned, A fluorine atom is preferable.

In addition, "alpha-position of hydroxy styrene" means the carbon atom which the benzene ring couple | bonds unless there is particular notice.

The structural unit derived from this hydroxy styrene is represented by following formula (b-1), for example.

[Formula 77]

In formula (b-1), R ^b1 represents a hydrogen atom, an alkyl group, a halogen atom or a halogenated alkyl group, R ^b2 represents an alkyl group having 1 to 5 carbon atoms, and p represents an integer of 1 or more and 3 or less. , q represents an integer of 0 or more and 2 or less.

The alkyl group of R ^b1 is preferably 1 to 5 carbon atoms. Moreover, a linear or branched alkyl group is preferable, and methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, etc. Can be mentioned. Among these, methyl group is preferable industrially.

As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned, A fluorine atom is preferable.

The halogenated alkyl group is a group in which part or all of the hydrogen atoms of the alkyl group having 1 to 5 carbon atoms described above are substituted with halogen atoms. Especially, the alkyl group in which all the hydrogen atoms were substituted by the fluorine atom is preferable. Moreover, a linear or branched fluorinated alkyl group is preferable, and trifluoromethyl group, hexafluoroethyl group, heptafluoropropyl group, nonafluorobutyl group, etc. are more preferable, and trifluoromethyl group (-CF ₃ ) Most preferred.

As R ^b1 , a hydrogen atom or a methyl group is preferable, and a hydrogen atom is more preferable.

^Examples of the alkyl group having 1 to 5 carbon atoms of R ^{b2 include} the same groups as in the case of R ^b1 .

q is an integer of 0 or more and 2 or less. Among these, it is preferable that it is 0 or 1, and it is preferable that it is especially 0 industrially.

When q is 1, any of ortho-position, meta-position, and para-position may be sufficient as substitution position of R <^b2> , and when q is 2, arbitrary substitution positions may be combined.

p is an integer of 1 or more and 3 or less, Preferably it is 1.

The substitution position of the hydroxyl group may be any of ortho-position, meta-position, and para-position when p is 1, but the para-position is preferred from the viewpoint of being readily available and inexpensive. In addition, when p is 2 or 3, arbitrary substitution positions can be combined.

The structural unit represented by said formula (b-1) can be used individually or in combination of 2 or more types.

It is preferable that the ratio of the structural unit derived from hydroxy styrene among polyhydroxy styrene resin is 60 mol% or more and 100 mol% or less with respect to all the structural units which comprise polyhydroxy styrene resin, and 70 mol% or more It is more preferable that it is 100 mol% or less, and it is further more preferable that it is 80 mol% or more and 100 mol% or less. By setting it in the said range, when it is set as the photosensitive composition, appropriate alkali solubility will be obtained.

It is preferable that polyhydroxy styrene resin further has a structural unit derived from styrene.

The term "structural unit derived from styrene" is defined herein to include a structural unit formed by cleaving ethylenic double bonds of styrene and styrene derivatives (however, hydroxystyrene is not included).

The "styrene derivative" includes derivatives in which a hydrogen atom bonded to the α-position of styrene is substituted with another substituent such as a halogen atom, an alkyl group, or a halogenated alkyl group, and an alkyl group having 1 to 5 carbon atoms in which the hydrogen atom of the phenyl group of styrene is It is defined to include derivatives substituted with substituents and the like.

As a halogen atom, a chlorine atom, a fluorine atom, a bromine atom, etc. are mentioned, A fluorine atom is preferable.

In addition, "alpha-position of styrene" means the carbon atom which the benzene ring couple | bonds unless there is particular notice.

The structural unit derived from this styrene is represented by a following formula (b-2), for example. In the formula, R ^b1 , R ^b2 and q have the same meanings as in the formula (b-1).

[Formula 78]

Roneun R ^b1 and R ^b2, there may be mentioned the formula (b1) of R ^b1 and R ^b2 as the same groups respectively.

q is an integer of 0 or more and 2 or less. Among these, it is preferable that it is 0 or 1, and it is preferable that it is especially 0 industrially.

When q is 1, any of ortho-position, meta-position, and para-position may be sufficient as substitution position of R <^b2> , and when q is 2, arbitrary substitution positions may be combined.

The structural unit represented by said formula (b-2) can be used individually or in combination of 2 or more types.

It is preferable that it is 40 mol% or less with respect to all the structural units which comprise polyhydroxy styrene resin, and, as for the ratio of the structural unit derived from styrene among polyhydroxy styrene resin, it is more preferable that it is 30 mol% or less, 20 It is more preferable that it is mol% or less. By setting it as said range, when it is set as the photosensitive composition, suitable alkali solubility will be obtained and the balance with another structural unit will become favorable.

In addition, the polyhydroxy styrene resin may have other structural units other than the structural unit derived from hydroxy styrene, and the structural unit derived from styrene. More preferably, the polyhydroxy styrene resin is a polymer composed only of structural units derived from hydroxy styrene, or a copolymer composed of structural units derived from hydroxy styrene and structural units derived from styrene.

Although the mass average molecular weight of polyhydroxy styrene resin is not specifically limited, 1,500 or more and 40,000 or less are preferable, and 2,000 or more and 8,000 or less are more preferable.

Moreover, novolak resin can also be used as alkali-soluble resin which has a phenolic hydroxyl group. This novolak resin can be obtained by addition condensation of phenols and aldehydes in the presence of an acid catalyst.

As phenols, Cresols, such as a phenol, o-cresol, m-cresol, and p-cresol; X, such as 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol Silenols; o-ethylphenol, m-ethylphenol, p-ethylphenol, 2-isopropylphenol, 3-isopropylphenol, 4-isopropylphenol, o-butylphenol, m-butylphenol, p-butylphenol, p- alkyl phenols such as tert-butylphenol; Trialkylphenols such as 2,3,5-trimethylphenol and 3,4,5-trimethylphenol; Polyhydric phenols such as resorcinol, catechol, hydroquinone, hydroquinone monomethyl ether, pyrogarol and fluoroglycinol; Alkyl polyhydric phenols such as alkylresolecin, alkyl catechol and alkylhydroquinone (the number of carbon atoms of the alkyl group contained in the alkyl polyhydric phenols is 1 or more and 4 or less); α-naphthol, β-naphthol, hydroxydiphenyl, bisphenol A and the like. These phenols can be used individually or in combination of 2 or more types.

Among these phenols, m-cresol and p-cresol are preferable, and it is more preferable to use m-cresol and p-cresol together. In this case, various characteristics, such as a sensitivity, can be adjusted by adjusting the compounding ratio of both.

Examples of the aldehydes include formaldehyde, paraformaldehyde, perfural, benzaldehyde, nitrobenzaldehyde, acetoaldehyde and the like. These aldehydes can be used individually or in combination of 2 or more types.

As an acid catalyst, Inorganic acids, such as hydrochloric acid, a sulfuric acid, nitric acid, phosphoric acid, a phosphoric acid; Organic acids such as formic acid, oxalic acid, acetic acid, diethyl sulfuric acid and paratoluenesulfonic acid; Metal salts such as zinc acetate; and the like. These acid catalysts can be used individually or in combination of 2 or more types.

As a novolak resin obtained in this way, a phenol / formaldehyde condensation novolak resin, a cresol / formaldehyde condensation novolak resin, a phenol- naphthol / formaldehyde condensation novolak resin, etc. are mentioned specifically ,.

Although the mass average molecular weight of novolak resin is not specifically limited, 1,000 or more and 30,000 or less are preferable, and 3,000 or more and 25,000 or less are more preferable.

Moreover, as alkali-soluble resin which has a phenolic hydroxyl group, phenol- xylene glycol condensation resin, cresol- xylene glycol condensation resin, phenol dicyclopentadiene condensation resin, etc. can also be used.

It is preferable that it is 20 mass% or more and 80 mass% or less with respect to solid content of the photosensitive composition of 3rd aspect, and, as for content of alkali-soluble resin which has a phenolic hydroxyl group, it is more preferable that they are 35 mass% or more and 65 mass% or less. By setting it as said range, there exists a tendency which is easy to obtain the balance of developability.

The acid crosslinkable substance in the photosensitive composition of the third aspect is not particularly limited, and a conventionally known acid crosslinkable substance can be used.

Specifically as an acid crosslinkable substance, amino resin which has a hydroxyl group or an alkoxyl group, for example, melamine resin, urea resin, guanamine resin, acetoguanamine resin, benzoguanamine resin, glycoluril-formaldehyde resin, succinyl Amide formaldehyde resin, ethylene urea-formaldehyde resin, etc. are mentioned. These acid crosslinkable substances are reacted with formalin in boiling water by melamine, urea, guanamine, acetoguanamine, benzoguanamine, glycoluril, succinylamide, and ethyleneurea in boiling water to form a methylol or lower alcohol. It can be easily obtained by making it react and alkoxylate. Practically, it can be obtained as melamine resins, such as Nikarak MX-750, Nikarak MW-30, and Nikarak MW100LM, and urea resins (all made by Sanwa Chemical Co., Ltd.), such as Nikarak MX-290. Moreover, benzoguanamine resins, such as Cymel 1123 and Cymel 1128 (made by Mitsui Cyanard), can also be obtained as a commercial item.

Alkoxy such as 1,3,5-tris (methoxymethoxy) benzene, 1,2,4-tris (isopropoxymethoxy) benzene, and 1,4-bis (sec-butoxymethoxy) benzene Phenol compounds which have a hydroxyl group, such as a benzene compound which has a real group, and 2, 6- dihydroxymethyl- p-tert- butylphenol, or an alkoxyl group, etc. can also be used. These acid crosslinkable substances can be used individually or in combination of 2 or more types.

It is preferable that they are 5 mass parts or more and 50 mass parts or less with respect to 100 mass parts of alkali-soluble resin which has a phenolic hydroxyl group, and, as for content of an acid crosslinkable substance, it is more preferable that they are 10 mass parts or more and 30 mass parts or less. By setting it as said range, curability and patterning characteristic of a photosensitive composition become favorable.

The photoacid generator in the photosensitive composition of the third aspect is not particularly limited, and a conventionally known photoacid generator can be used. As a preferable photo-acid generator, the photo-acid generator demonstrated about the 2nd photosensitive composition is mentioned.

It is preferable that it is 0.05 mass part or more and 30 mass parts or less with respect to 100 mass parts of alkali-soluble resin which has a phenolic hydroxyl group, and, as for content of a photo-acid generator, it is more preferable that they are 0.1 mass part or more and 10 mass parts or less. By setting it as said range, curability of the photosensitive composition will become favorable.

The photosensitive composition of a 3rd aspect contains a hydrogen barrier agent (B) as above. When this compound is contained in the photosensitive composition, pattern formation which has a hydrogen barrier performance is attained.

As for content of a hydrogen barrier agent (B), 0.01 mass% or more and 30 mass% or less are preferable with respect to the mass of resin corresponded to the base material component (A) in the photosensitive composition of 3rd aspect, and 0.05 mass% or more and 20 mass% % Or less is more preferable, and 0.1 mass% or more and 10 mass% or less are especially preferable. By setting it as said range, the pattern which has hydrogen barrier performance can be obtained, obtaining favorable developability.

The photosensitive composition of a 3rd aspect may further contain the compound of less than 2,000 molecular weight which has 4 or more of phenolic hydroxyl groups.

Specific examples of such compounds include bis [2-hydroxy-3- (2 '), in addition to benzophenone compounds such as various tetrahydroxybenzophenones, pentahydroxybenzophenones, hexahydroxybenzophenones, and heptahydroxybenzophenones. -Hydroxy-5'-methylbenzyl) -5-methylphenyl] methane, bis (4-hydroxy-3,5-dimethylphenyl) -3,4-dihydroxyphenylmethane, bis (4-hydroxy-2 , 5-dimethylphenyl) -3,4-dihydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) -2,4-dihydroxyphenylmethane, bis (4-hydroxy-2 , 5-dimethylphenyl) -2,4-dihydroxyphenylmethane, bis (3-cyclohexyl-4-hydroxy-6-methylphenyl) -3,4-dihydroxyphenylmethane, bis (3-cyclohexyl Hydroxy, such as -6-hydroxy-4-methylphenyl) -3,4-dihydroxyphenylmethane and bis (4-hydroxy-2,3,5-trimethylphenyl) -3,4-dihydroxyphenylmethane Oxyaryl compound; 2- (2,3,4-trihydroxyphenyl) -2- (2 ', 3', 4'-trihydroxyphenyl) propane, 2- (2,4-dihydroxyphenyl) -2- ( Bis (hydroxyphenyl) alkane type compounds, such as 2 ', 4'- dihydroxyphenyl) propane; Poly (o-hydroxystyrene), poly (m-hydroxystyrene), poly (p-hydroxystyrene), poly (α-methyl-p-hydroxystyrene), poly (4-hydroxy) with molecular weight less than 2,000 Polyhydroxy styrene compounds such as -3-methyl styrene); Etc. can be mentioned. These benzophenone compounds, hydroxyaryl compounds, bis (hydroxyphenyl) alkane compounds, and polyhydroxystyrene compounds may have substituents other than hydroxyl groups.

These compounds can be used individually or in combination of 2 or more types.

It is preferable that content of the compound of molecular weight less than 2,000 which has four or more phenolic hydroxyl groups is 0.5 mass part or more and 5 mass parts or less with respect to 100 mass parts of alkali-soluble resin which has a phenolic hydroxyl group. By setting it as said range, the phenomenon which the tip at the time of patterning the photosensitive composition can be suppressed can be suppressed.

As an organic solvent in the photosensitive composition of a 3rd aspect, the organic solvent illustrated by the photosensitive composition of a 1st aspect is mentioned.

The content of the organic solvent is preferably in an amount of from 1% by mass to 50% by mass, more preferably from 5% by mass to 30% by mass.

The photosensitive composition of a 3rd aspect may contain said various additives as needed, similarly to the photosensitive composition of a 1st aspect.

(4) The photosensitive composition of the fourth aspect

The photosensitive composition of a 4th aspect contains an epoxy compound and a hydrogen barrier agent (B), and may further contain the organic solvent arbitrarily.

As an epoxy compound in the photosensitive composition of a 4th aspect, the same thing as the epoxy compound mentioned as the above-mentioned epoxy resin precursor is mentioned, for example.

It is preferable that it is 55 mass% or more and 99 mass% or less with respect to solid content of the photosensitive composition of a 4th aspect, and, as for content of an epoxy compound, it is more preferable that they are 70 mass% or more and 95 mass% or less. By setting it as said range, coating-film formation ability can be improved.

The photosensitive composition of a 4th aspect contains the hydrogen barrier agent (B) mentioned above. Since a hydrogen barrier agent (B) is a compound containing an imidazole ring, when it is exposed, hardening of an epoxy compound is accelerated | stimulated and it provides a favorable patterning characteristic and hydrogen barrier performance to a photosensitive composition.

It is preferable that content of a hydrogen barrier agent (B) is 0.01 mass part or more and 30 mass parts or less with respect to 100 mass parts of epoxy compounds, 0.05 mass part or more and 20 mass parts or less are more preferable, 0.1 mass part or more and 10 mass parts or less Particularly preferred. By setting it as said range, patterning characteristic and hydrogen barrier performance can be acquired.

As an organic solvent in the photosensitive composition of a 4th aspect, the organic solvent illustrated by the photosensitive composition of a 1st aspect is mentioned. Among them, propylene glycol monomethyl ether, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl acetate, propylene glycol monomethyl ether acetate, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, γ Polar solvents such as butyrolactone, aromatic hydrocarbons such as toluene, and mixed solvents thereof are preferable.

The content of the organic solvent in the case of containing the organic solvent is preferably an amount such that the solid content concentration of the photosensitive composition of the fourth aspect is 1% by mass or more and 50% by mass or less, and the amount of 5% by mass or more and 30% by mass or less More preferred.

The photosensitive composition of a 4th aspect may contain said various additives as needed similarly to the photosensitive composition of a 1st aspect.

In addition, the epoxy group containing polycarboxylic acid resin in 5th aspect mentioned later is not limited that all epoxy groups are consumed by reaction with "monocarboxylic acid which has an alcoholic hydroxyl group", and "polybasic anhydride", and usually the epoxy group which remains Since it has a branch, it also corresponds to the epoxy resin in the photosensitive composition of a 4th aspect. In this regard, the epoxy group-containing polycarboxylic acid resin in the photosensitive composition of the fourth aspect may be used as the epoxy resin in the photosensitive composition of the fourth aspect. In this specification, resin other than the epoxy group containing polycarboxylic acid resin in the photosensitive composition of a 4th aspect may be called noncarboxylic acid modified epoxy resin among the epoxy resins in the photosensitive composition of a 4th aspect.

(5) The photosensitive composition of the fifth aspect

The photosensitive composition of a 5th aspect is a negative photosensitive composition containing an epoxy-group containing polycarboxylic acid resin, a photo-acid generator, a hydrogen barrier agent (B), and an organic solvent.

As the epoxy group-containing polycarboxylic acid resin in the photosensitive composition of the fifth aspect, for example, a reactant obtained by reacting an epoxy compound having two or more epoxy groups in one molecule and a monocarboxylic acid having one or more alcoholic hydroxyl groups in one molecule In addition, resin obtained by making polybasic acid anhydride react can be used.

As an epoxy compound which has two or more epoxy groups in 1 molecule, the thing similar to the epoxy compound mentioned as an epoxy resin precursor mentioned above, and the above-mentioned epoxy group containing resin is mentioned, for example. Especially, a novolak-type epoxy resin, a bisphenol-type epoxy resin, a trisphenol methane type epoxy resin, a tris (2, 3- epoxypropyl) isocyanurate, a biphenyl diglycidyl ether, an alicyclic epoxy resin, a copolymer type Epoxy resin etc. are mentioned.

As a novolak-type epoxy resin, the phenols, such as phenol, cresol, a halogenated phenol, an alkylphenol, and the novolak obtained by reacting formaldehyde under an acidic catalyst, for example, epichlorohydrin and methyl epichlorohydrin are reacted. The epoxy resin etc. which are obtained by making it carry out are mentioned. As a commercial item, EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1027, EPPN-201, BREN-S (all are the Nippon Kayaku Co., Ltd. make); DEN-431, DEN-439 (all manufactured by Dow Chemical Company); N-730, N-770, N-865, N-665, N-673, VH-4150 (all are the Dainippon Ink & Chemicals Co., Ltd. product) etc. are mentioned.

As a bisphenol-type epoxy resin, For example, the epoxy resin obtained by making bisphenols, such as bisphenol A, bisphenol F, bisphenol S, tetrabrom bisphenol A, epichlorohydrin, and methyl epichlorohydrin react, bisphenol A, The epoxy resin etc. which are obtained by making diglycidyl ether of bisphenol F, the condensate of the said bisphenol, epichlorohydrin, and methyl epichlorohydrin react, are mentioned. As a commercial item, Epicoat 1004, Epicoat 1002, Epicoat 4002, Epicoat 4004 (all are from Yucca shell epoxy company), etc. are mentioned.

As a trisphenol methane type epoxy resin, the epoxy resin obtained by making trisphenol methane, a triscresol methane, epichlorohydrin, and methyl epichlorohydrin react, for example is mentioned. As a commercial item, EPPN-501, EPPN-502 (all are the Nippon Kayaku Co., Ltd.), etc. are mentioned.

As an alicyclic epoxy resin, the thing similar to the alicyclic epoxy compound mentioned above is mentioned. As a commercial item, Ceroxide 2021 by Daicel Chemical Industries Ltd .; Epomic VG-3101 made by Mitsui Petrochemical Industries, Ltd .; E-1031S by the Yucca shell epoxy company, EPB-13 by the Nippon Soda company, EPB-27, etc. are mentioned. Moreover, as a copolymer type epoxy resin, CP-50M, CP-50S made by Nippon Yushi Co., Ltd. which is a copolymer of glycidyl methacrylate, styrene, and (alpha) -methylstyrene, or glycidyl methacrylate, and cyclohexyl maleimide Copolymers, such as these, etc. are mentioned.

As an especially preferable example of the epoxy resin which has two or more epoxy groups in these 1 molecule, a cresol novolak-type epoxy resin, a phenol novolak-type epoxy resin, a bisphenol-type epoxy resin, a trisphenol methane type epoxy resin, etc. are mentioned, for example. have. In particular, polycondensates of α-hydroxyphenyl-ω-hydropoly (biphenyldimethylene-hydroxyphenylene) and 1-chloro-2,3-epoxy propane and α-2,3-epoxypropoxyphenyl-ω -Hydropoly {2- (2,3-epoxypropoxy) -benzylidene-2,3-epoxypropoxyphenylene} is preferred.

As monocarboxylic acid which has one or more alcoholic hydroxyl groups in 1 molecule, For example, hydroxy, such as dimethylol propionic acid, dimethylol acetic acid, dimethylol butyric acid, dimethylol valeric acid, dimethylol caproic acid, and hydroxy pivaric acid Monocarboxylic acids are mentioned. Among these, the monocarboxylic acid which has 1 or more and 5 or less alcoholic hydroxyl groups in 1 molecule is preferable.

Examples of the polybasic acid anhydride include succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydro phthalic anhydride, hexahydro phthalic anhydride, methylendmethylenetetrahydro phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like. have.

0.1 mol or more and 0.7 mol or less of monocarboxylic acid are preferable with respect to 1 equivalent of epoxy groups of an epoxy compound, and, as for reaction of the said epoxy compound and the said monocarboxylic acid, 0.2 mol or more and 0.5 mol or less are more preferable. In this reaction, it is preferable to use the organic solvent which does not have a hydroxyl group or a carboxyl group which does not react with an epoxy compound or polybasic acid anhydride. In addition, a catalyst (e.g., triphenylphosphine, benzyldimethylamine, trialkylammonium chloride, triphenylstyrene, etc.) may be used to promote the reaction. In the case of using a catalyst, inactivation of the catalyst using an organic peroxide or the like after the completion of the reaction is particularly preferable because of its stability and good shelf life. 0.1 mass% or more and 10 mass% or less are preferable with respect to a reaction mixture, and, as for the usage-amount of a reaction catalyst, 60 degreeC or more and 150 degrees C or less are preferable. Thereby, the reactant of the said epoxy compound and the said monocarboxylic acid can be obtained.

In reaction of this reactant and polybasic acid anhydride, it is preferable to make the polybasic acid anhydride of the amount which the acid value of the epoxy group containing polycarboxylic acid resin finally obtained become 50 mgKOH / g or more and 150 mgKOH / g or less. As for reaction temperature, 60 degreeC or more and 150 degrees C or less are preferable. In this manner, an epoxy group-containing polycarboxylic acid resin can be obtained.

These epoxy group containing polycarboxylic acid resin can be used individually or in combination of 2 or more types.

It is preferable that it is 30 mass% or more and 80 mass% or less with respect to solid content of the photosensitive composition of 5th aspect, and, as for content of epoxy group containing polycarboxylic acid resin, it is more preferable that they are 40 mass% or more and 70 mass% or less. By setting it as said range, coating-film formation ability can be improved.

As a photo-acid generator in the photosensitive composition of a 5th aspect, the photo-acid generator illustrated by the photosensitive composition of a 2nd aspect is mentioned.

It is preferable that it is 0.5 mass% or more and 30 mass% or less with respect to solid content of the photosensitive composition of 5th aspect, and, as for content of a photo-acid generator, it is more preferable that they are 1 mass% or more and 20 mass% or less. By setting it as said range, curability of the photosensitive composition will become favorable.

The photosensitive composition of a 5th aspect contains a hydrogen barrier agent (B) as above. When this compound is contained in the photosensitive composition, pattern formation which has a hydrogen barrier performance is attained.

As for content of a hydrogen barrier agent (B), 0.01 mass% or more and 30 mass% or less are preferable with respect to the mass of resin corresponded to the base material component (A) in the photosensitive composition of 5th aspect, and 0.05 mass% or more and 20 mass% % Or less is more preferable, and 0.1 mass% or more and 10 mass% or less are especially preferable. By setting it as said range, the pattern which has hydrogen barrier performance can be obtained, obtaining favorable developability.

The photosensitive composition of 5th aspect may contain the modification component for adjusting moisture resistance, heat resistance, adhesiveness, etc. further. This modification component may be cured by itself, heat or ultraviolet rays, or may react with the residual hydroxyl group or carboxyl group of the epoxy group-containing polycarboxylic acid resin by heat or ultraviolet rays or the like. Specifically, an epoxy compound having one or more epoxy groups in one molecule, melamine derivatives (for example, hexamethoxymelamine, hexabutoxylated melamine, condensed hexamethoxymelamine, etc.), bisphenol A compounds (for example, Tetramethylol bisphenol A etc.), an oxazoline compound, etc. are mentioned.

As an epoxy compound which has one or more epoxy groups in 1 molecule, Epicoat 1009, 1031 (all are from Yucca shell company), Epikron N-3050, N-7050 (all are the Dainippon Ink & Chemicals Co., Ltd. product), DER-642U, DER Bisphenol-A epoxy resins, such as -673MF (all are the Dow Chemical Company make); Hydrogenated bisphenol A epoxy resins such as ST-2004 and ST-2007 (all manufactured by Totokasei Co., Ltd.); Bisphenol F type epoxy resins, such as YDF-2004 and YDF-2007 (all are the Totokasei Co., Ltd.); Brominated bisphenol A epoxy resins such as SR-BBS, SR-TBA-400 (all manufactured by Sakamoto Pharmaceutical Co., Ltd.), YDB-600, and YDB-715 (all manufactured by Totokasei Co., Ltd.); Novolak-type epoxy resins such as EPPN-201, EOCN-103, EOCN-1020, and BREN (all manufactured by Nippon Kayaku Co., Ltd.); Novolak-type epoxy resins of bisphenol A, such as Epikron N-880 by Dainippon Ink and Chemicals, Inc .; Rubber modified epoxy resins such as Epikron TSR-601 manufactured by Dainippon Ink and Chemicals, Inc. and R-1415-1 manufactured by ACR; Bisphenol S-type epoxy resins, such as EBPS-200 by Nippon Kayaku Co., Ltd. and Epiklon EXA-1514 by Dainippon Ink Chemical Co., Ltd .; Diglycidyl terephthalate such as Nippon Oil Holding Co., Ltd., primer DGT; Triglycidyl isocyanurate such as TEPIC manufactured by Nissan Kagaku Corporation; Bixylenol type epoxy resins, such as YX-4000 by Yucca shell company; Bisphenol-type epoxy resins such as YL-6056 manufactured by Yucca Shell; Alicyclic epoxy resins such as ceroxide 2021 manufactured by Daicel Chemical Industries, Ltd .; Etc. can be mentioned.

It is preferable that it is 50 mass% or less with respect to solid content of the photosensitive composition of 5th aspect, and, as for content of a modification component, it is more preferable that it is 30 mass% or less.

The photosensitive composition of a 5th aspect may further contain a coloring agent similarly to the photosensitive composition of a 1st aspect.

As an organic solvent in the photosensitive composition of a 5th aspect, the organic solvent illustrated by the photosensitive composition of a 1st aspect is mentioned.

The content of the organic solvent is preferably an amount of 1% by mass or more and 50% by mass or less, and more preferably 5% by mass or more and 30% by mass or less of the solid content concentration of the photosensitive composition of the fifth aspect.

The composition for hydrogen barrier film formation or the photosensitive composition of the 1st-5th aspect may contain various additives as needed. As an additive, a sensitizer, a hardening accelerator, a filler, an adhesive agent, antioxidant, a ultraviolet absorber, an aggregation inhibitor, a thermal polymerization inhibitor, an antifoamer, a leveling agent, surfactant, a thickener, etc. are mentioned.

As a sensitizer, the anthracene compound (9,10- dialkoxy anthracene derivative) which has an alkoxy group in 9-position and 10-position, for example is preferable. Examples of the alkoxy group include an alkoxy group having 1 to 4 carbon atoms. The 9,10- dialkoxy anthracene derivative may further have a substituent. As a substituent, a halogen atom, a C1 or more alkyl group, a sulfonic acid alkylester group, a carboxylic acid alkylester group, etc. are mentioned. Examples of the alkyl group in the sulfonic acid alkyl ester group and the carboxylic acid alkyl ester group include an alkyl group having 1 to 4 carbon atoms. The substitution position of these substituents is preferably 2-position.

As a 9, 10- dialkoxy anthracene derivative, for example, 9, 10- dimethoxy anthracene, 9, 10- diethoxy anthracene, 9, 10- dipropoxy canthracene, 9, 10- dimethoxy-2-ethyl Anthracene, 9,10-diethoxy-2-ethylanthracene, 9,10-dipropoxy-2-ethylanthracene, 9,10-dimethoxy-2-chloroanthracene, 9,10-dimethoxyanthracene-2-sulfonic acid Methyl ester, 9, 10- diethoxy anthracene 2-sulfonic acid methyl ester, 9, 10- dimethoxy anthracene 2-carboxylic acid methyl ester, etc. are mentioned.

These compounds are treated with a reducing agent such as zinc powder, hydrosulfide, palladium-carbon and sodium borohydride in an aqueous alkali solution with anthraquinone derivatives to form 9,10-dihydroxyanthracene derivatives, followed by dimethyl sulfate, Sulfate esters such as diethyl sulfate, toluene sulfonic acid methyl, toluene sulfonic acid ethyl, toluene sulfonic acid propyl, toluene sulfonic acid esters such as toluene sulfonic acid monoethylene glycol ester, or benzene sulfonic acid esters such as methyl benzene sulfonate, ethyl benzene sulfonate and benzene sulfonic acid propyl It is obtained by alkoxylation of 9, 10-position.

These sensitizers can be used individually or in combination of 2 or more types.

When each composition contains a photo-acid generator, it is preferable that it is 0.1 or more and 6 or less in molar ratio with respect to a photo-acid generator, and, as for content of a sensitizer, it is more preferable that it is 0.2 or more and 4 or less. By setting it as said range, the sensitivity and hardenability of each composition will become favorable.

Examples of the filler include known fillers such as barium sulfate, barium titanate, silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide and mica.

It is preferable that it is 60 mass% or less with respect to solid content of each composition, and, as for content of a filler, it is more preferable that they are 5 mass% or more and 40 mass% or less.

As surfactant, BM-1000, BM-1100 (all made by BM Chemi Corporation), mega pack F142D, mega pack F172, mega pack F173, mega pack F183 (all made by Nippon Ink Chemical Co., Ltd.), fluoride FC-135 Fluoride FC-170C, Fluoride FC-430, Fluoride FC-431 (all manufactured by Sumitomo 3M), Surflon S-112, Surflon S-113, Surfron S-131, Surflon S-141, Commercially available fluorine-based surfactants such as SUPRON S-145 (all manufactured by Asahi Glass Co., Ltd.), SH-28PA, SH-190, SH-193, SZ-6032, SF-8428 (all manufactured by Toray Silicone Co., Ltd.). However, it is not limited to these.

Examples of the thickener include ultra finely divided silica and montmorillonite.

Examples of the antifoaming agent and / or leveling agent include silicone polymers, fluorine polymers, and the like.

As an adhesive imparting agent, a silane coupling agent etc. are mentioned.

Moreover, the composition for hydrogen barrier film formation or the photosensitive composition of the 1st-5th aspect is 1- (N, N-di (2-ethylhexyl) amino) methyl-1H- benzotriazole, 1- as arbitrary additives. (N, N-di (2-ethylhexyl) amino) methyl-1H-methylbenzotriazole, carboxybenzotriazole, benzotriazole, methylbenzotriazole, dihydroxypropylbenzotriazole, bisaminomethylbenzotriazole You may use benzotriazole derivatives, such as a sol, individually or in combination of 2 or more types.

The addition amount of the said various additive which the composition for hydrogen barrier film formation or the photosensitive composition of 1st-5th aspect may contain is 0.001 mass% or more 10 with respect to the whole composition except the case where it states specially, for example. What is necessary is just to adjust suitably in the range of mass% or less, Preferably they are 0.1 mass% or more and 5 mass% or less.

<Preparation method of the photosensitive composition>

The photosensitive composition is prepared by mixing each said component with a stirrer. Moreover, you may filter using a membrane filter etc. so that the prepared photosensitive composition may become uniform.

<Method for producing hydrogen barrier film>

The hydrogen barrier film containing a hydrogen barrier agent (B) can be formed by using the hydrogen barrier film formation composition containing the hydrogen barrier agent (B) demonstrated above.

The composition for forming a hydrogen barrier film includes a polyacetal resin, a polyamide resin, a polycarbonate resin, a polyester resin (polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polyarylate, etc.) as the base component (A), FR-AS resin, FR-ABS resin, AS resin, ABS resin, polyphenylene oxide resin, polyphenylene sulfide resin, polysulfone resin, polyether sulfone resin, polyether ether ketone resin, fluorine resin, polyimide resin, Polyamideimide resin, polyamidebismaleimide resin, polyetherimide resin, polybenzoxazole resin, polybenzothiazole resin, polybenzoimidazole resin, silicone resin, BT resin, polymethylpentene, ultra high molecular weight polyethylene, FR Resin materials such as polypropylene, (meth) acrylic resins (e.g., polymethyl methacrylate, etc.) and polystyrene For the case that also is as described above with respect to hydrogen-barrier film forming method.

When the composition for hydrogen barrier film formation contains a thermosetting material as a base component (A), after forming the hydrogen barrier film formation composition by methods, such as application | coating, a film formed is heated at the temperature according to the kind of curable material. By hardening, it can form a hydrogen barrier film.

When the composition for forming a hydrogen barrier film is the above-mentioned various photosensitive compositions, typically, the method for forming a coating film by applying the composition for forming a hydrogen barrier film on a substrate and exposing the coating film A hydrogen barrier film is produced.

More specifically, first, a coating film is formed by an appropriate coating method. For example, by applying and drying the photosensitive composition on a substrate using a contact transfer type coating device such as a roll coater, a reverse coater, a bar coater, a non-contact type coating device such as a spinner (rotary coating device), a curtain flow coater, and the like, A film can be formed.

The drying method is not particularly limited, and for example, (1) prebaking is carried out between 60 seconds and 120 seconds at a temperature of 80 ° C or more and 120 ° C or less, preferably 90 ° C or more and 100 ° C or less on a hot plate. The method of (2) the method of leaving to stand at room temperature for several hours or more and several days or less, (3) the method of removing a solvent by putting in a warm air heater or an infrared heater for tens of minutes or more for several hours or less.

Next, an electromagnetic wave is irradiated and exposed to a coating film selectively positionally. When the photosensitive composition is a negative photosensitive composition which hardens | cures by exposure, you may expose to the whole surface of a coating film.

When performing exposure selectively, the electromagnetic wave may be irradiated through a positive or negative mask, or may be irradiated directly. Although exposure amount changes with the composition of the photosensitive composition, about 5 mJ / cm <^2> or more and about 500 mJ / cm <^2> or less are preferable, for example.

When the exposure is performed on the entire surface of the coating film, the exposed coating film can be used as it is as a hydrogen barrier film.

When the exposure is performed in a position-selective manner, a hydrogen barrier film patterned into a desired shape is obtained by developing the coated film after exposure with a developer.

The image development method is not specifically limited, For example, an immersion method, a spray method, etc. can be used. Examples of the developing solution include organic developing solutions such as monoethanolamine, diethanolamine and triethanolamine, and aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia and quaternary ammonium salts.

About the patterned hydrogen barrier film after image development, it is preferable to perform postbaking at about 200 degreeC or more and about 250 degrees C or less.

The hydrogen barrier film formed as mentioned above is used without particular limitation for various uses for which shielding of hydrogen gas is required, and is particularly suitably used in an electronic device described later.

In addition, since the hydrogen barrier film can suppress the permeation of hydrogen gas having a small molecular weight and a molecular size, the permeation of a gas having a larger molecular size than hydrogen can also be suppressed. Examples of such gas include nitrogen gas, oxygen gas, ozone gas, water vapor, carbon monoxide gas, carbon dioxide gas, nitrogen oxide gas and sulfur oxide gas.

<Electronic device>

The hydrogen barrier film formed using the hydrogen barrier film formation composition demonstrated above is used suitably in the electronic device provided with a passivation film.

The passivation film is a film provided to protect functional layers such as semiconductor layers from ions, gases, physical damage, and the like.

Although it does not specifically limit as an electronic element, The organic electronic element provided with an organic conductive layer, an organic semiconductor layer, an organic light emitting layer, etc. is mentioned preferably.

As a suitable specific example of an electronic element, light emitting elements, such as an LED element and an organic electroluminescent element, a semiconductor element, a solar cell element, and a solid-state image sensor are mentioned.

The passivation film includes, for example, a metal oxide, a metal nitride, a metal carbide, a metal oxynitride, a metal oxide carbide, or the like. More specifically, oxides, nitrides, carbides, oxynitrides or oxycarbides containing at least one metal selected from Si, Al, In, Sn, Zn, Ti, Cu, Ce and Ta are preferably used.

Among these materials, oxides, nitrides or oxynitrides of metals selected from Si, Al, In, Sn, Zn and Ti are preferred, oxides or nitrides of Si or Al are more preferred, and silicon nitride (Si nitride) is particularly preferred. desirable.

These may contain another element as a secondary component. For example, silicon nitride may be hydrogen oxynitride including hydrogen, and may further be hydrogen oxynitride silicon including oxygen.

The oxide film or nitride film of Si may be an oxide film or a nitride film by firing a coating film of a silicon-containing polymer-containing composition such as polysilazane, polysiloxane, polysiloxane, or polysilane.

In terms of the protective performance of the passivation film, the passivation film preferably contains silicon nitride (SiN).

The passivation film demonstrated above may contain hydrogen gas or the compound which can generate | generate hydrogen gas, such as ammonia and amines, based on the raw material and the manufacturing method. The passivation film containing silicon nitride is particularly easy to generate hydrogen gas.

On the other hand, electronic devices often include TFTs to drive the devices like organic EL devices. In addition, the electronic device is often provided with wiring made of metal such as copper.

The TFT may be impaired in function due to a reduction reaction by contact with hydrogen gas, and there is a fear that the electrical characteristics may change due to reduction by hydrogen gas also in the metal wiring.

However, when the electronic device includes a hydrogen barrier film together with the passivation film, the hydrogen gas generated from the passivation film can be shielded with the hydrogen barrier film, and generation of adverse effects in the member affected by the hydrogen gas can be suppressed.

It is preferable that a hydrogen barrier film is provided between the object to be protected from hydrogen, such as TFT, and the generation source of hydrogen, for example.

When hydrogen present in the external environment of the electronic device is likely to invade the object to be protected in the electronic device, a hydrogen barrier agent is added to the hard coat layer provided on the surface where the electronic device is in contact with the external environment to form a hydrogen barrier film. You may also do it.

Moreover, when protecting the protection object, such as TFT in an electronic element, from the hydrogen which generate | occur | produces from the film used as a hydrogen generation source, such as a passivation film, it is preferable that a hydrogen barrier film is formed between the film used as a hydrogen generation source and a protection object. In this case, for example, the planarization film may be a hydrogen barrier film.

As described above, in an electronic device having a passivation film, providing a hydrogen barrier film can protect a member that may be adversely affected by hydrogen, such as TFT or metal wiring, thereby manufacturing an electronic device having high reliability of operation. Can be.

EXAMPLE

EXAMPLES Hereinafter, although an Example is shown and this invention is demonstrated further more concretely, the scope of the present invention is not limited to these Examples.

Synthesis Example 1 Synthesis of Compound Represented by Formula (1) 1

[Formula 79]

Compound A (2.00 g, 8.12 mmol) and methanol (20 g) were added to a 50 ml three-necked flask, followed by nitrogen replacement, followed by heating at 60 ° C. with a water bath to dissolve Compound A. Next, diazabicyclo undecene (DBU; 1.24 g, 8.12 mmol) was dripped according to the said scheme, and it was made to react at 60 degreeC for 4 hours. After completion of the reaction, the mixture was cooled to room temperature (25 ° C), and then the solvent was distilled off from the reaction solution using a rotary evaporator to obtain the compound (Compound 1) represented by the formula (1). (Amount = 3.27 g, yield = 95%, yellow viscous liquid)

¹ H-NMR (heavy DMSO, 400 MHz): cation δ (ppm) = 3.48 (CH ₂ , 2H), 3.40 (CH ₂ , 2H), 3.15 (CH ₂ , 2H), 2.65 (CH ₂ , 2H), 1.82 (CH ₂ , 2H), 1.70-1.45 (CH ₂ , 6H),

Anion δ (ppm) = 7.70 (CH, 1H), 7.22 (Ph, 2H), 7.15 (CH, 1H), 6.85 (Ph, 2H), 6.80 (CH, 1H), 5.63 (CH, 1H), 3.70 ( CH ₃ , 3H), 2.85-2.65 (CH ₂ , 2H)

Synthesis Example 2 Synthesis of Compound Represented by Formula (1) 2

[Formula 80]

Compound A (2.00 g, 8.12 mmol) and methanol (20 g) were added to a 50 ml three-necked flask, followed by nitrogen replacement, followed by heating at 60 ° C. with a water bath to dissolve Compound A. Next, diazabicyclononene (DBN; 1.11 g, 8.12 mmol) was added dropwise and reacted at 60 ° C for 4 hours according to the above scheme. After completion | finish of reaction, after cooling to room temperature, the compound (compound 2) represented by said Formula (1) was obtained by distilling a solvent off using a rotary evaporator. (Amount = 2.91 g, yield = 90%, yellow viscous liquid)

¹ H-NMR (heavy DMSO, 400 MHz): cation δ (ppm) = 3.55 (CH ₂ , 2H), 3.40-3.25 (CH ₂ , 4H), 2.81 (CH ₂ , 2H), 2.00 (CH ₂ , 2H ), 1.88 (CH ₂ , 2H)

Anion δ (ppm) = 7.70 (CH, 1H), 7.22 (Ph, 2H), 7.15 (CH, 1H), 6.85 (Ph, 2H), 6.80 (CH, 1H), 5.63 (CH, 1H), 3.70 ( CH ₃ , 3H), 2.85-2.65 (CH ₂ , 2H)

Synthesis Example 3 Synthesis of Compound Represented by Formula (1) 3

[Formula 81]

Compound A (2.00 g, 8.12 mmol) and methanol (20 g) were added to a 50 ml three-necked flask, followed by nitrogen replacement, followed by heating at 60 ° C. with a water bath to dissolve Compound A. Next, imidazole (IM; 0.55 g, 8.12 mmol) was added and reacted at 60 degreeC for 4 hours. After completion | finish of reaction, after cooling to room temperature, the compound (compound 3) represented by said Formula (1) was obtained by distilling a solvent off using a rotary evaporator. (Amount = 2.43 g, yield = 95%, white solid)

¹ H-NMR (Medium DMSO, 400 MHz): Cationic δ (ppm) = 7.03 (CH, 2H), 7.65 (CH, 1H)

Anion δ (ppm) = 7.86 (CH, 1H), 7.35 (3H), 6.99 (3H), 5.70 (CH, 1H), 3.71 (CH ₃ , 3H), 3.35-3.16 (CH ₂ , 2H)

About compound A single substance, imidazole single substance, and obtained compound 3 which are raw materials, respectively using the X-ray-diffraction measuring apparatus (made by Rigaku Corporation; brand name "Full automatic horizontal multipurpose X-ray diffraction measuring apparatus SmartLab"), The X-ray diffraction pattern was measured under the conditions. Obtained compound 3 is not a simple mixture, but is judged to be a salt from the point which showed the reflection pattern different from each single body which is a raw material.

* X-ray used: CuKα ray derived from swivel cathode X-ray source, 45 kV-200mA

* Scanning speed (2θ): 4.0 ° / min

* Divergence Slit: (2/3) °

Scattering Slit: (2/3) °

In addition, we follow standard condition setting of package measurement "general purpose measurement> general purpose (intensive method)".

Synthesis Example 4 Synthesis of Compound Represented by Formula (1) 4

[Formula 82]

Compound A (1.60 g, 6.50 mmol) and tetrahydrofuran (3 g) were added to a 20 ml Naus flask and nitrogen-substituted, and then heated at 60 ° C. in an oil bath to dissolve Compound A. Next, 7-methyl-1,5,7-triazabicyclo [4.4.0] deca-5-ene (MTBD; 1.00 g, 6.50 mmol) was added dropwise and reacted at 60 ° C for 30 minutes according to the above scheme. After completion | finish of reaction, after cooling to room temperature, the compound (compound 4) represented by said Formula (1) was obtained by distilling a solvent off using the rotary evaporator. (Amount = 2.5 g, yield = 95%, yellow viscous liquid)

¹ H-NMR (medium DMSO, 500 MHz): cation δ (ppm) = 9.20 (NH, 1H), 3.27-3.22 (6H), 3.17-3.15 (2H), 2.90 (CH ₃ , 3H), 1.92-1.89 (2H), 1.81-1.79 (2H)

Anion δ (ppm) = 7.67 (CH, 1H), 7.21 (2H), 7.12 (1H), 6.84 (2H), 6.79 (1H), 5.62 (CH, 1H), 3.71 (CH ₃ , 3H), 2.73- 2.61 (CH ₂ , 2H)

Synthesis Example 5 Synthesis of Compound Represented by Formula (1) 5

[Formula 83]

Compound A (1.60 g, 6.50 mmol) and methanol (9 g) were added to a 20 mL Naus flask and nitrogen-substituted, and then heated at 60 ° C. in an oil bath to dissolve Compound A. Next, 1,5,7-triazabicyclo [4.4.0] deca-5-ene (TBD; 0.85 g, 6.09 mmol) was added dropwise and reacted at 60 ° C for 30 minutes according to the above scheme. After completion of the reaction, the mixture was cooled to room temperature and then the solvent was distilled off using a rotary evaporator to obtain a compound (Compound 5) represented by the formula (1) (amount = 2.2 g, yield = 95%, yellow). solid)

¹ H-NMR (heavy DMSO, 500 MHz): cation δ (ppm) = 10.48 (NH, 2H), 3.22-3.17 (4H), 3.10-3.07 (4H), 1.86-1.81 (4H)

Anion δ (ppm) = 7.71 (CH, 1H), 7.25 (2H), 7.17 (1H), 6.86 (2H), 6.80 (1H), 5.65 (CH, 1H), 3.71 (CH ₃ , 3H), 2.87- 2.73 (CH ₂ , 2H)

Synthesis Example 6 Synthesis of Compound Represented by Formula (1) 6

[Formula 84]

Compound A (1.50 g, 6.09 mmol) and methanol (9 g) were added to a 20 mL Naus flask and nitrogen-substituted, and then heated at 60 ° C. in an oil bath to dissolve Compound A. Next, 1,1,3,3-tetramethylguanidine (TMG; 0.7 g, 6.09 mmol) was added dropwise and reacted at 60 ° C for 30 minutes according to the above scheme. After completion | finish of reaction, after cooling to room temperature, the compound (compound 6) represented by said Formula (1) was obtained by distilling a solvent off using a rotary evaporator. (Amount = 2.2 g, yield = 100%, yellow solid)

¹ H-NMR (medium DMSO, 500 MHz): Cationic δ (ppm) = 2.84 (6H)

Anion δ (ppm) = 7.67 (CH, 1H), 7.21 (2H), 7.12 (1H), 6.85 (2H), 6.79 (1H), 5.62 (CH, 1H), 3.71 (CH ₃ , 3H), 2.28- 2.64 (CH ₂ , 2H)

Synthesis Example 7 Synthesis of Compound Represented by Formula (1) 7

[Formula 85]

Compound A (1.00 g, 4.06 mmol) and methanol (9 g) were added to a 20 mL Naus flask and nitrogen-substituted, and then heated at 60 ° C. in an oil bath to dissolve Compound A. Next, iminotris (dimethylamino) phosphorane (0.72 g, 4.06 mmol) was added dropwise according to the above scheme and reacted at 60 ° C for 30 minutes. After completion | finish of reaction, after cooling to room temperature, the compound (compound 7) represented by said formula was obtained by distilling a solvent off using the rotary evaporator for a reaction liquid. (Amount = 1.7 g, yield = 98%, yellow solid)

¹ H-NMR (medium DMSO, 500 MHz): cation δ (ppm) = 2.63 (9H), 2.61 (9H),

Anion δ (ppm) = 7.65 (CH, 1H), 7.18 (2H), 7.10 (1H), 6.84 (2H), 6.84 (1H), 5.61 (CH, 1H), 3.71 (CH ₃ , 3H), 2.28- 2.64 (CH ₂ , 2H)

Example 1

12 parts by mass of alkali-soluble resin having the following structure, 6 parts by mass of dipentaerythritol hexaacrylate, 1.0 part by mass of a photopolymerization initiator having the following structure, and a surface conditioner (BYK-310, polyester-modified polydimethylsiloxane, manufactured by Big Chemi Japan Co., Ltd.) 0.04 mass part and 2.0 mass parts of hydrogen barrier agents (compound 3 mentioned above) were melt | dissolved in the mixed solvent, and the processable composition was obtained.

As a mixed solvent, the mixed solvent which consists of 45 mass parts of propylene glycol monomethyl ethers, 30 mass parts of diethylene glycol monomethyl ethers, and N, N, N ', N'-tetramethylurea was used.

The structure of alkali-soluble resin, the structure of a photoinitiator, and the structure of a hydrogen barrier agent are described below. About alkali-soluble resin, the number of the lower right of each structural unit is content (mass%) of each structural unit in resin.

[Formula 86]

After apply | coating the obtained photosensitive composition on the SiN board | substrate (the laminated body which has a SiN layer on a silicon wafer) with a spin coater, the coating film was prebaked at 105 degreeC for 100 second. The prebaked coating film was exposed all over at an exposure dose of 50 mJ / cm ² using an ultraviolet curing machine (ghi line broadband) to cure the coating film. The cured film with a film thickness of 2.0 micrometers was obtained by post-baking the coating film after exposure for 20 minutes at 230 degreeC.

About the SiN substrate provided with a cured film, the silicon wafer side was heated, and the component (hydrogen radical or hydrogen ion) of molecular weight 1 and molecular weight which generate | occur | produce from the surface of a cured film by a thermal deposition spectrometry (TDS) method. The quantity of the component (hydrogen gas) of 2 and the component (water vapor) of molecular weight 18 was measured.

The heating at the time of the measurement of gas generation amount was performed by heating up from 50 degreeC to 280 degreeC at the speed of 10 degree-C / min. Heating was complete | finished when it reached 280 degreeC.

The amount of generation (peak intensity) of these gases is shown in Table 1.

Comparative Example 1

About the SiN substrate in which the cured film was not formed, it carried out similarly to Example 1, and measures the generation amount of the component (hydrogen radical or hydrogen ion) of molecular weight 1, the component (hydrogen gas) of molecular weight 2, and the component (water vapor) of molecular weight 18. It was.

The amount of generation (peak intensity) of these gases is shown in Table 1.

The amount of generated gas is the amount of generated gas from the SiN surface.

Comparative Example 2

Except not using a hydrogen barrier agent, it carried out similarly to Example 1, and obtained the photosensitive composition. Using the obtained photosensitive composition, in the same manner as in Example 1, a cured film was formed on a SiN substrate.

About the SiN substrate provided with a cured film, it carried out similarly to Example 1, and measured the generation amount of the component (hydrogen radical or hydrogen ion) of molecular weight 1, the component (hydrogen gas) of molecular weight 2, and the component (water vapor) of molecular weight 18. .

The amount of generation (peak intensity) of these gases is shown in Table 1.

Comparative Example 3

A photosensitive composition was obtained in the same manner as in Example 1 except that a commercially available molecular powder was added to the photosensitive composition so that the ratio in the solid content was 20% by mass, and dispersed to be uniform. Using the obtained photosensitive composition, in the same manner as in Example 1, a cured film was formed on a SiN substrate.

About the SiN substrate provided with a cured film, it carried out similarly to Example 1, and measured the generation amount of the component (hydrogen radical or hydrogen ion) of molecular weight 1, the component (hydrogen gas) of molecular weight 2, and the component (water vapor) of molecular weight 18. .

The generation amount (peak intensity) of these gases is shown in [Table 1].

According to a comparison between Example 1 and Comparative Examples 1 and 2, when a cured film is formed on a SiN substrate using a photosensitive composition containing a hydrogen barrier agent having a predetermined structure, permeation of gas generated from SiN is applied to the cured film. It turns out that it can suppress effectively by this.

On the other hand, according to the comparison between Comparative Example 3 and Comparative Examples 1 and 2, even when a material capable of adsorbing hydrogen gas or water such as molecular sieve is added to the cured film formed by using the photosensitive composition, SiN It can be seen that the permeation of the gas generated from the film can hardly be suppressed by the cured film.

<Examples 2-4, Comparative Examples 4-5>

Example 2

The composition for hydrogen barrier film formation was obtained like Example 1 except having used the resin which substituted the epoxy group containing structural unit of alkali-soluble resin of Example 1 with the structural unit derived from glycidyl methacrylate.

[Comparative Example 4]

Except not having used the hydrogen barrier agent of the said structure, it carried out similarly to Example 2, and obtained the film forming composition for comparison.

Example 3

A hydrogen barrier film was formed in the same manner as in Example 1 except that the resin in which the epoxy group-containing structural unit of the alkali-soluble resin of Example 1 was substituted with a structural unit derived from 3,4-epoxycyclohexylmethylmethacrylate was used. The composition was obtained.

[Comparative Example 5]

Except not having used the hydrogen barrier agent of the said structure, it carried out similarly to Example 3, and obtained the film forming composition for comparison.

Example 4

Except having made 0.6 mass part addition amounts of the hydrogen barrier agent of Example 1, it carried out similarly to Example 1, and obtained the composition for hydrogen barrier film formation.

After each obtained composition was coated on a SiN substrate (laminate having a SiN layer on a silicon wafer), the coating film was prebaked at 80 ° C. for 100 seconds. The prebaked coating film was exposed all over at an exposure dose of 50 mJ / cm ² using an ultraviolet curing machine (ghi line broadband) to cure the coating film. The cured film with a film thickness of 2.0 micrometers was obtained by post-baking the coating film after exposure for 20 minutes at 230 degreeC. Called cured films 2-4 and comparative cured films 4-5, respectively.

When the amount of generation of each gas was compared with respect to the obtained SiN substrate provided with each cured film in the same manner as in Example 1, in the cured films 2 to 3 according to the examples, gas permeation was more effectively achieved than the corresponding comparative cured films 4 to 5. Could be restrained. Moreover, also in the cured film 4 which concerns on an Example, permeation | transmission of gas was able to be suppressed more effectively than the comparative example 2. As shown in FIG.

<Examples 5-6, Comparative Examples 6-7>

Example 5

As a base component, 100 mass parts of compounds represented by following formula (A-2), the hardening agent represented by 1 mass part of following formula (a1-2-1), and 10 mass parts hydrogen barrier agent (compound 3 mentioned above) It mixed and obtained the composition for hydrogen barrier film formation.

[Formula 87]

[Formula 88]

Comparative Example 6

Except not using a hydrogen barrier agent, it carried out similarly to Example 5, and obtained the film forming composition for comparison.

Example 6

A hydrogen barrier film-forming composition was obtained in the same manner as in Example 5 except that 100 parts by mass of the compound represented by the following formula (A-3) was used instead of the compound represented by the formula (A-2).

[Formula 89]

Comparative Example 7

Except not using a hydrogen barrier agent, it carried out similarly to Example 6, and obtained the film formation composition for comparison.

Each obtained composition was coated on a SiN substrate (a laminate having a SiN layer on a silicon wafer), and then subjected to full surface exposure (ghi line broadband) at an exposure dose of 50 mJ / cm ² using an ultraviolet curing machine to obtain a film thickness of about 2.0 μm. A cured film was obtained. Called cured films 5-6 and comparative cured films 6-7, respectively.

When the amount of generation of each gas was compared with respect to the obtained SiN substrate provided with each cured film in the same manner as in Example 1, in the cured films 5 to 6 according to the examples, gas permeation was more effectively achieved than the corresponding comparative cured films 6 to 7. Could be restrained.

<Examples 7-8, Comparative Examples 8-9>

Example 7

As a base material, 100 mass parts of mixed resin components (mass ratio (A-3) :( A-4) = 70: 30) represented by a following formula (A-3) and a following formula (A-4), and a following formula ( 5 parts by mass of a curing agent (naphthalic acid derivative) represented by a1-2-2) and 15 parts by mass of a hydrogen barrier agent (compound 3 described above) were mixed using 700 parts by mass of propylene glycol monomethyl ether acetate to obtain a hydrogen barrier. The film forming composition was obtained.

[Formula 90]

[Formula 91]

[Formula 92]

Comparative Example 8

Except not using a hydrogen barrier agent, it carried out similarly to Example 7, and obtained the film forming composition for comparison.

Example 8

As a base material component, the mixed resin component was made into 100 mass parts of mixed resin components (mass ratio (A-5) :( A-6) = 70: 30) represented by following formula (A-5) and following formula (A-6). A hydrogen barrier film-forming composition was obtained in the same manner as in Example 7 except for the above.

[Formula 93]

[Formula 94]

Comparative Example 9

Except not using a hydrogen barrier agent, it carried out similarly to Example 8, and obtained the film forming composition for comparison.

After each obtained composition was coated on a SiN substrate (laminate having a SiN layer on a silicon wafer), the coating film was prebaked at 80 ° C. for 120 seconds. The prebaked coating film was exposed all over at an exposure dose of 50 mJ / cm ² using an ultraviolet curing machine (ghi line broadband) to cure the coating film. The cured film with a film thickness of 2.0 micrometers was obtained by baking the coating film after exposure for 20 minutes at 100 degreeC. Called cured films 7-8 and comparative cured films 8-9, respectively.

About the SiN board | substrate provided with each obtained cured film, the generation amount of each gas was compared similarly to Example 1, but in cured films 7-8 which concern on an Example, compared with the corresponding cured film 8-9 more effectively, Permeation could be suppressed.

Claims (8)

Formula (1) below:

(In formula (1), X ^{m <+>} represents a m-valent counter cation, R <^1> represents the aromatic group which may have a substituent, R <^2> represents the alkylene group which may have a substituent, R <^3> represents a halogen atom, a hydroxyl group, Mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfonic acid ester group, phosphino group, phosphinyl group, phosphonic acid ester group or organic group, m represents an integer of 1 or more, n is An integer of 0 or more and 3 or less, and R ² may be bonded to R ¹ to form a cyclic structure.)
Hydrogen barrier agent which consists of a compound represented by. The composition for hydrogen barrier film formation containing a base material component (A) and the hydrogen barrier agent (B) of Claim 1. The method according to claim 2,
The said base material component (A) contains alkali-soluble resin (A1) and a photopolymerizable compound (A2),
Furthermore, the composition for hydrogen barrier film formation containing a photoinitiator (C). The hydrogen barrier film containing the hydrogen barrier agent (B) of Claim 1. The hydrogen barrier film which consists of hardened | cured material of the composition for hydrogen barrier film formation of Claim 3. Forming a coating film by applying the composition for forming a hydrogen barrier film of claim 3 onto a substrate;
A method of producing a hydrogen barrier film comprising exposing the coating film. An electronic device comprising a passivation film and a hydrogen barrier film of claim 4 or 5. The method according to claim 7,
An electronic device further comprising a TFT.